CN116891563A

CN116891563A - Polymerizable composition for optical material, polymerizable prepolymer composition for optical material, cured product, and method for producing optical material

Info

Publication number: CN116891563A
Application number: CN202310815368.2A
Authority: CN
Inventors: 末杉幸治; 伊藤伸介; 中野将太郎; 松井勇辅
Original assignee: Mitsui Chemicals Inc
Current assignee: Mitsui Chemicals Inc
Priority date: 2020-01-27
Filing date: 2021-01-27
Publication date: 2023-10-17
Also published as: US20230051738A1; CN116874733A; KR20210116710A; JPWO2021153632A1; MX2021013149A; KR20220138004A; EP3919967A4; CN113557256B; WO2021153632A1; CN113557256A; US20220041789A1; CN116874734A; JP7141529B2; JP2022036209A; US11542357B2; EP3919967A1

Abstract

The present application relates to a polymerizable composition for optical materials, a polymerizable prepolymer composition for optical materials, a cured product, and a method for producing optical materials. A polymerizable composition for optical materials, which comprises 2 or more different monomers for optical materials, and a polymerization catalyst, wherein at least 1 of the 2 or more different monomers for optical materials is an isocyanate compound having no aromatic ring, the content of the polymerization catalyst is greater than 0.05 parts by mass and 2.0 parts by mass or less relative to 100 parts by mass of the total of the 2 or more different monomers for optical materials, and the viscosity of the polymerizable composition for optical materials measured by a type B viscometer at 25 ℃ and 60rpm is 10 to 1000 mPas.

Description

Polymerizable composition for optical material, polymerizable prepolymer composition for optical material, cured product, and method for producing optical material

The present application is a divisional application of the application application of 2021, 1, 27, 202180002443.2, entitled "polymerizable composition for optical Material, polymerizable prepolymer composition for optical Material, cured product, and method for producing optical Material".

Technical Field

The present disclosure relates to a polymerizable composition for optical materials, a polymerizable prepolymer composition for optical materials, a cured product, and a method for producing optical materials.

Background

As a method for producing a resin usable for an optical material for a plastic lens, for example, a cast polymerization method in which a polymerizable composition containing a monomer is injected into a mold (casting mold) and heat-cured is used.

In the casting polymerization method, a polymerizable composition is prepared and degassed, and then the polymerizable composition is injected into a mold (casting mold), and the resultant is heated and cured (polymerization reaction) to take out (release) the mold and annealed to obtain an optical material (for example, a lens, a semi-finished blank (semi-finished blank), or the like).

In the heat curing, in order to improve the quality of the optical material, the polymerization reaction is usually performed for several hours to several tens of hours while gradually increasing the temperature by heating, and specifically, it takes about 20 hours to 48 hours. In addition, it is known that much time (for example, 9 out of the total time) in the total time of the manufacturing process is spent on the time for polymerization.

In the example of patent document 1, it is described that: the mold into which the polymerizable composition was injected was gradually heated from 10℃to 120℃and polymerized for 20 hours, thereby obtaining a molded article.

In addition, in the example of patent document 2, it is described that: the temperature of the mold filled with the polymerizable composition was gradually raised from 25℃to 120℃over 16 hours, and the mold was heated at 120℃for 4 hours to obtain a molded article.

Patent document 1: international publication No. 2014/027427

Patent document 2: international publication No. 2014/133111

Disclosure of Invention

Problems to be solved by the invention

As described above, in the conventional process of producing an optical material, polymerization is generally performed over a period of several hours to several tens of hours (for example, about 20 hours to 48 hours) while gradually increasing the temperature by heating.

However, since the time for manufacturing the optical material is long, it is necessary to operate the device for manufacturing for a long time, which is an economic burden and deteriorates the operation efficiency.

On the other hand, when an optical material is produced by the conventional method, if the polymerization reaction is performed by shortening the heating polymerization time, the polymerization is insufficient, and therefore, there is a possibility that the optical material is not cured, or defects such as striae occur in the optical material even if the optical material is cured, and the quality of the optical material is degraded.

Based on the above, in the production of an optical material, it is required to shorten the production time of the optical material while maintaining the quality of the obtained optical material.

An object of an embodiment of the present disclosure is to provide a method for producing an optical material, which can reduce the production time of the optical material while maintaining the quality of the optical material obtained.

Further, an object of one embodiment of the present disclosure is to provide a polymerizable composition for an optical material that can be used in a method for producing an optical material, which can maintain the quality of the obtained optical material and can shorten the production time of the optical material.

Means for solving the problems

Specific means for solving the above-described problems include the following means.

Embodiment 1 of the present disclosure includes the following means.

1 > a polymerizable composition for an optical material, which comprises 2 or more different monomers for an optical material, at least 1 of which is an isocyanate compound having no aromatic ring, and a polymerization catalyst, wherein the content of the polymerization catalyst is greater than 0.05 parts by mass and 2.0 parts by mass or less relative to 100 parts by mass of the total of the 2 or more different monomers for an optical material, and the viscosity of the polymerizable composition for an optical material is 10 to 1000 mPas measured by a B-type viscometer at 25 ℃ and 60 rpm.

A polymerizable composition for optical materials, which has a thixotropic ratio (thixotropy) of 1.3 or less, as described in < 2 > and < 1 >.

< 3 > the polymerizable composition for optical materials described as < 1 > or < 2 >, comprising: 2 or more different monomers for optical materials; a polymerization catalyst; and a prepolymer having a polymerizable functional group, wherein the prepolymer is a polymer of the aforementioned 2 or more different monomers for an optical material.

The polymerizable composition for optical materials according to any one of < 4 > to < 1 > - < 3 >, wherein the 2 or more different monomers for optical materials contain at least 1 active hydrogen compound selected from the group consisting of a polythiol compound having 2 or more mercapto groups, a hydroxythiol compound containing 1 or more mercapto groups and 1 or more hydroxyl groups, a polyol compound containing 2 or more hydroxyl groups, and an amine compound.

The polymerizable composition for optical materials according to any one of < 5 > to < 1 > to < 4 >, wherein the polymerization catalyst satisfies the following condition 1.

[ condition 1]

Ea/R is-7100 or more and-2900 or less.

(Ea is the reaction rate constant of the monomer for 2 or more different optical materials at 2 or more different temperatures, the activation energy calculated by an Arrhenius curve, and R is the gas constant (8.314J/mol/K))

The polymerizable composition for optical materials according to any one of < 6 > to < 1 > to < 5 >, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of basic catalysts having a pKa value of 4 to 8 and organometallic catalysts.

The polymerizable composition for optical materials according to any one of < 6-1 > to < 1 > wherein the polymerization catalyst comprises at least 1 selected from the group consisting of an amine-based catalyst and an organotin-based catalyst.

The polymerizable composition for optical materials according to any one of < 6-2 > to < 1 > - < 6-1 >, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of 3, 5-lutidine, 2,4, 6-collidine, triethylenediamine, N-dimethylethanolamine, N-ethylmorpholine, dibutyltin dichloride, dimethyltin dichloride, dibutyltin dilaurate and dibutyltin diacetate.

< 7 > a polymerizable prepolymer composition for optical materials comprising: a prepolymer having a polymerizable functional group, the prepolymer being a polymer of 2 or more different monomers for an optical material; and a polymerization catalyst, wherein at least 1 of the 2 or more different monomers for an optical material is an isocyanate compound having no aromatic ring, and the viscosity of the polymerizable prepolymer composition for an optical material is 10 mPas to 2000 mPas measured by a B-type viscometer at 25 ℃ and 60 rpm.

The polymerizable prepolymer composition for optical materials according to claim 8 < 7, wherein the content of the polymerization catalyst is 0.1 to 4.0 parts by mass based on 100 parts by mass of the total of the prepolymers.

A polymerizable prepolymer composition for optical materials having a thixotropic ratio of 1.3 or less, wherein the polymerizable prepolymer composition is < 8-1 > as defined in < 7 > or < 8 >.

The polymerizable prepolymer composition for optical materials according to any one of < 8-2 > to < 7 > - < 8-1 >, wherein the prepolymer contains an isocyanate group.

The polymerizable prepolymer composition for optical materials according to any one of < 8-3 > to < 7 > - < 8-1 >, wherein the prepolymer contains substantially no isocyanate groups.

The polymerizable prepolymer composition for optical materials according to any one of < 9 > to < 7 > - < 8-3 >, wherein the 2 or more different monomers for optical materials contain at least 1 active hydrogen compound selected from the group consisting of a polythiol compound having 2 or more mercapto groups, a hydroxythiol compound containing 1 or more mercapto groups and 1 or more hydroxyl groups, a polyol compound containing 2 or more hydroxyl groups, and an amine compound.

The polymerizable prepolymer composition for optical materials according to any one of < 10 > to < 7 > to < 9 >, wherein the polymerization catalyst satisfies the following condition 1.

[ condition 1]

Ea/R is-7100 or more and-2900 or less.

The polymerizable prepolymer composition for optical materials according to any one of < 11 > to < 7 > to < 10 >, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of basic catalysts having a pKa value of 4 to 8 and organometallic catalysts.

The polymerizable prepolymer composition for optical materials according to any one of < 11-1 > to < 7 > wherein the polymerization catalyst comprises at least 1 selected from the group consisting of amine-based catalysts and organotin-based catalysts.

The polymerizable prepolymer composition for optical materials according to any one of < 11-2 > to < 7 > - < 11-1 >, wherein a value obtained by subtracting the refractive index B of a prepolymer raw material composition, which is a composition before formation of the prepolymer and contains the above 2 or more different monomers for optical materials and a polymerization catalyst, from the refractive index A of the polymerizable prepolymer composition for optical materials is larger than 0.

A cured product of the polymerizable composition for an optical material according to any one of < 12 > to < 6-2 > or the polymerizable prepolymer composition for an optical material according to any one of < 7 > to < 11-2 >.

The cured product of < 12-1 > the < 12 > is a cured product of the polymerizable composition for an optical material, wherein the 2 or more different monomers for an optical material contain at least 1 active hydrogen compound selected from the group consisting of a polythiol compound having 2 or more mercapto groups, a hydroxythiol compound containing 1 or more mercapto groups and 1 or more hydroxyl groups, a polyol compound containing 2 or more hydroxyl groups, and an amine compound.

The cured product of < 12-2 > or < 12-1 > is a cured product of the polymerizable composition for an optical material, wherein the polymerization catalyst satisfies the following condition 1.

[ condition 1]

Ea/R is-7100 or more and-2900 or less.

The cured product of any one of < 12 > < 12 to < 12-2 > which is a cured product of the polymerizable composition for an optical material, wherein the polymerizable composition for an optical material contains at least 1 selected from the group consisting of a basic catalyst having a pKa value of 4 to 8 and an organometallic catalyst.

The cured product of any one of < 12 > < 12 to < 12-3 > which is a cured product of the polymerizable composition for an optical material, wherein the polymerizable composition for an optical material contains at least 1 kind selected from the group consisting of amine-based catalysts and organotin-based catalysts.

The cured product of any one of < 12-5 > to < 12-4 > which is a cured product of the polymerizable composition for an optical material, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of 3, 5-lutidine, 2,4, 6-collidine, triethylenediamine, N-dimethylethanolamine, N-ethylmorpholine, dibutyltin dichloride, dimethyltin dichloride, dibutyltin dilaurate and dibutyltin diacetate.

A method for producing an optical material, comprising the steps of:

A preparation step of preparing a polymerizable composition for an optical material, the polymerizable composition for an optical material containing 2 or more different monomers for an optical material; and a catalyst for the polymerization, wherein the catalyst comprises,

at least 1 of the 2 or more different optical material monomers is an isocyanate compound having no aromatic ring, and the content of the polymerization catalyst is more than 0.05 parts by mass and 2.0 parts by mass or less relative to 100 parts by mass of the total of the 2 or more different optical material monomers; and

and a curing step of curing the polymerizable composition for an optical material by polymerizing the 2 or more different monomers for an optical material in the polymerizable composition for an optical material.

A method for producing an optical material, comprising the steps of:

a preparation step of preparing a total of 100 parts by mass of 2 or more different monomers for optical materials and 0.010 to 2.0 parts by mass of a polymerization catalyst; and

a prepolymer step of mixing at least a part of the 2 or more different monomers for optical materials with at least a part of the polymerization catalyst, polymerizing at least a part of the 2 or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer,

At least 1 of the above 2 or more different monomers for optical materials is an isocyanate compound having no aromatic ring.

The method for producing an optical material according to claim 15 or 14, further comprising the steps of:

a step of producing a polymerizable composition for optical materials, wherein at least the remaining part of the 2 or more different monomers for optical materials is added to a mixture containing the prepolymer, thereby obtaining a polymerizable composition for optical materials containing the 2 or more different monomers for optical materials, the prepolymer, and the polymerization catalyst; and

and a curing step of curing the 2 or more different monomers for optical materials in the polymerizable composition for optical materials to obtain an optical material as a cured product of the polymerizable composition for optical materials.

The method for producing an optical material according to any one of < 16 > to < 13 > - < 15 >, wherein the 2 or more different monomers for an optical material contain at least 1 active hydrogen compound selected from the group consisting of a polythiol compound having 2 or more mercapto groups, a hydroxythiol compound containing 1 or more mercapto groups and 1 or more hydroxyl groups, a polyol compound containing 2 or more hydroxyl groups, and an amine compound.

The method for producing an optical material according to any one of < 17 > to < 13 > to < 16 >, wherein the polymerization catalyst satisfies the following condition 1.

[ condition 1]

Ea/R is-7100 or more and-2900 or less.

The method for producing an optical material according to any one of < 18 > to < 13 > to < 17 >, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of a basic catalyst having a pKa value of 4 to 8 and an organometallic catalyst.

The method for producing an optical material according to any one of < 19 > to < 13 > to < 18 >, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of an amine-based catalyst and an organotin-based catalyst.

And < 20 > a cured product of 2 or more different optical monomers, wherein at least 1 of the 2 or more different optical monomers is an isocyanate compound having no aromatic ring, no beads having a length of 1.0mm or more are present within a radius of 15mm from the center of the cured product, and the amine content is 0.03 mass% or more and 2.5 mass% or less as measured by gas chromatography mass spectrometry.

ADVANTAGEOUS EFFECTS OF INVENTION

According to one embodiment of the present disclosure, a method for producing an optical material can be provided that can satisfactorily shorten the production time of the optical material while maintaining the quality of the optical material obtained.

Further, according to another embodiment of the present disclosure, a polymerizable composition for an optical material that can be used in a method for producing an optical material, which can maintain the quality of the obtained optical material and can satisfactorily shorten the production time of the optical material, can be provided.

According to one embodiment of the present disclosure, a method for producing an optical material can be provided, which can maintain the quality of the obtained optical material and can shorten the production time of the optical material.

Further, according to one embodiment of the present disclosure, a polymerizable composition for an optical material that can be used in a method for producing an optical material, which can maintain the quality of the obtained optical material and can shorten the production time of the optical material, can be provided.

By one embodiment of the present disclosure, a method for manufacturing an optical material can be provided that can suppress striae in the obtained optical material and can shorten the manufacturing time of the optical material.

Further, according to one embodiment of the present disclosure, a polymerizable composition for an optical material that can be used in a method for producing an optical material, which can suppress striae in the obtained optical material and can shorten the production time of the optical material, can be provided.

Drawings

FIG. 1 is a graph showing the relationship between the time elapsed for the polymerization reaction and the temperature in the heat-insulated container in example 8A.

Detailed Description

In the present disclosure, a numerical range indicated by "to" is used to indicate a range including numerical values described before and after "to" as a lower limit value and an upper limit value.

In the present disclosure, when a plurality of substances belonging to each component are present in a composition, the amount of each component in the composition refers to the total amount of the plurality of substances present in the composition unless specifically stated.

In the numerical ranges described in stages in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stages. In addition, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the embodiment.

In the present disclosure, the term "process" refers not only to an independent process but also to a process that is not clearly distinguishable from other processes, as long as the desired purpose of the process is achieved.

The present disclosure includes embodiment 1 and embodiment 2.

Each embodiment will be described.

Embodiment 1 to the upper limit

Polymerizable composition for optical Material

The polymerizable composition for an optical material according to embodiment 1 is a polymerizable composition for an optical material comprising 2 or more different monomers for an optical material, at least 1 of which is an isocyanate compound having no aromatic ring, and a polymerization catalyst, wherein the content of the polymerization catalyst is greater than 0.05 parts by mass and 2.0 parts by mass or less based on 100 parts by mass of the total of the 2 or more different monomers for an optical material, and the viscosity of the polymerizable composition for an optical material is 10 to 1000mpa·s measured with a B-type viscometer at 25 ℃ and 60 rpm.

The polymerizable composition for an optical material according to embodiment 1 can maintain the quality of the obtained optical material and can favorably shorten the production time of the optical material by including the above-described constitution.

(monomer for optical Material)

The polymerizable composition for an optical material of embodiment 1 contains 2 or more different monomers for an optical material, and at least 1 of the monomers for an optical material is an isocyanate compound having no aromatic ring.

The monomer for optical material is not particularly limited as long as it is a monomer that can be used for optical applications.

For example, a monomer that can be used for producing an optical material having any of the following properties may be used.

The total light transmittance of the optical material obtained by using the monomer for optical material may be 10% or more. The total light transmittance of the optical material may be measured in accordance with JIS K7361-1 (1997).

The haze (i.e., total haze) of the optical material obtained using the monomer for an optical material may be 10% or less, preferably 1% or less, and more preferably 0.5% or less. The haze of the optical material was measured at 25℃according to JIS-K7105 using a haze measuring machine (available from Tokyo electric color Co., ltd., TC-HIIIDPK).

The refractive index of the optical material obtained using the monomer for optical material is preferably 1.58 or more. The refractive index of the optical material obtained using the optical material monomer may be 1.80 or less and may be 1.75 or less. The refractive index of the optical material may be measured in accordance with JIS K7142 (2014).

The shape of the optical material obtained using the optical material monomer is not particularly limited, and may be plate-like, cylindrical, rectangular parallelepiped, or the like.

As the monomer for an optical material, a polymerizable monomer that is polymerized when a polymerization catalyst described later is used can be mentioned. Specifically, isocyanate compounds, polythiol compounds having 2 or more mercapto groups, hydroxythiol compounds containing 1 or more mercapto groups and 1 or more hydroxyl groups, polyol compounds containing 2 or more hydroxyl groups, amine compounds, and the like are exemplified.

The above-mentioned 2 or more different monomers for optical materials preferably contain at least 1 active hydrogen compound selected from the group consisting of polythiol compounds having 2 or more mercapto groups, hydroxythiol compounds containing 1 or more mercapto groups and 1 or more hydroxyl groups, polyol compounds containing 2 or more hydroxyl groups, and amine compounds.

[ isocyanate Compound ]

Examples of the isocyanate compound include aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, heterocyclic isocyanate compounds, and the like, and 1 or a mixture of 2 or more kinds of the isocyanate compounds may be used. These isocyanate compounds may comprise dimers, trimers, prepolymers. Examples of the isocyanate compound include those exemplified in international publication No. 2011/055540.

Further, as the isocyanate compound, halogen substituents (for example, chlorine substituents, bromine substituents, etc.), alkyl substituents, alkoxy substituents, carbodiimide-modified substances, urea-modified substances, biuret-modified substances of the above-mentioned compounds can also be used,

prepolymer-type modified products of the above-mentioned compounds with nitro substituents, polyols and the like,

dimerization or trimerization reaction products of the above-mentioned compounds, and the like.

These compounds may be used alone or in combination of 2 or more.

In the present disclosure, the alicyclic isocyanate compound means an isocyanate compound having an alicyclic structure and may have a structure other than the alicyclic structure, such as a heterocyclic structure.

The aromatic isocyanate compound means an isocyanate compound which contains an aromatic structure and may contain any one of an aliphatic structure, an alicyclic structure and a heterocyclic structure or a combination thereof.

The heterocyclic isocyanate compound is an isocyanate compound having a heterocyclic structure and not having an alicyclic structure or an aromatic structure.

The aliphatic isocyanate compound is an isocyanate compound having no aromatic structure, alicyclic structure or heterocyclic structure.

The isocyanate compound preferably contains at least 1 selected from the group consisting of aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds and heterocyclic isocyanate compounds.

At least 1 of the monomers for an optical material in embodiment 1 is an isocyanate compound having no aromatic ring. Specific examples of the isocyanate compound having no aromatic ring include alicyclic isocyanate compound having no aromatic ring, heterocyclic isocyanate compound, and aliphatic isocyanate compound. The alicyclic isocyanate compound, the heterocyclic isocyanate compound, and the aliphatic isocyanate compound having no aromatic ring are preferable in that the polymerization reaction rate is not excessively high and the polymerization reaction is easily controlled as compared with the isocyanate compound having an aromatic ring.

The monomer for an optical material may contain an isocyanate compound other than the isocyanate compound having no aromatic ring.

When the monomer for an optical material contains an isocyanate compound having no aromatic ring and an isocyanate compound having an aromatic ring, the ratio of the isocyanate compound having no aromatic ring to the isocyanate compound having an aromatic ring is preferably in the range of 7:3 to 10:0, more preferably in the range of 8:2 to 10:0, in terms of the molar ratio of isocyanate groups, from the viewpoint of controlling the polymerization reaction.

The isocyanate compound other than the isocyanate compound having no aromatic ring is not particularly limited, and examples thereof include isocyanate compounds having an aromatic ring. When the monomer for an optical material contains an isocyanate compound having no aromatic ring and an isocyanate compound having an aromatic ring, the number of moles of isocyanate groups in the isocyanate compound having no aromatic ring is preferably larger than the number of moles of isocyanate groups in the isocyanate compound having an aromatic ring.

In embodiment 1, the isocyanate compound preferably contains at least 1 selected from isophorone diisocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, m-xylylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, dicyclohexylmethane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, 1, 6-hexamethylene diisocyanate, and 1, 5-pentanediisocyanate from the viewpoint of maintaining the quality of the optical material and shortening the production time of the optical material,

More preferably comprises at least 1 selected from isophorone diisocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, dicyclohexylmethane diisocyanate, and 1, 3-bis (isocyanatomethyl) cyclohexane,

further preferably, at least 1 selected from the group consisting of 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, dicyclohexylmethane diisocyanate, and 1, 3-bis (isocyanatomethyl) cyclohexane is contained.

[ active hydrogen Compound ]

Examples of the active hydrogen compound include a polythiol compound having 2 or more mercapto groups, a hydroxythiol compound containing 1 or more mercapto groups and 1 or more hydroxyl groups, a polyol compound containing 2 or more hydroxyl groups, and an amine compound.

As the active hydrogen compound, an oligomer of the above active hydrogen compound, a halogen substituent (for example, a chlorine substituent, a bromine substituent, or the like) of the above active hydrogen compound can be used.

The active hydrogen compounds may be used alone or in combination of 2 or more.

(polythiol Compound having 2 or more mercapto groups)

As the polythiol compound having 2 or more mercapto groups, there may be mentioned a compound exemplified in International publication No. 2016/125736.

In embodiment 1, the polythiol compound preferably contains at least one member selected from the group consisting of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, pentaerythritol tetrakis (3-mercaptopropionate), bis (mercaptoethyl) sulfide, pentaerythritol tetrakis (2-mercaptoacetate), 2, 5-bis (mercaptomethyl) -1, 4-dithiacyclohexane, 1, 3-tetrakis (mercaptomethylthio) propane, 4, 6-bis (mercaptomethylthio) -1, 3-dithiahexane, 2- (2, 2-dithiaethyl) -1, 3-dithiabutane,

more preferably at least 1 selected from the group consisting of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), and 2, 5-bis (mercaptomethyl) -1, 4-dithiahexane,

It is further preferable to contain at least 1 selected from the group consisting of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane and pentaerythritol tetrakis (3-mercaptopropionate).

(polythiol Compound having 3 or more mercapto groups)

As the active hydrogen compound, a polythiol compound having 3 or more mercapto groups may be mentioned.

In the case where the polymerizable composition for an optical material according to embodiment 1 contains a polythiol compound having 3 or more mercapto groups as an active hydrogen compound, from the viewpoint of promoting the polymerization reaction, a compound (also referred to as a compound (N1)) obtained by replacing at least 1 mercapto group of 3 or more mercapto groups contained in the polythiol compound having 3 or more mercapto groups with a group represented by the following formula (N1) is preferable.

[ chemical formula 1]

In formula (N1), the bonding position is represented.

In the polymerizable composition for an optical material according to embodiment 1, when the peak area is measured by high performance liquid chromatography from the viewpoint of easiness of adjustment of polymerization reaction, the peak area of the compound (N1) is preferably 3.0 or less, more preferably 1.5 or less, relative to the peak area 100 of the polythiol compound having 3 or more mercapto groups.

In the case of measuring the peak area by high performance liquid chromatography, the peak area of the compound (N1) is preferably 0.01 or more relative to the peak area 100 of the polythiol compound having 3 or more mercapto groups, from the viewpoint of promoting the polymerization reaction.

The peak area by high performance liquid chromatography can be measured by the method described in paragraph 0146 of International publication No. 2014/027665.

(hydroxythiol compound having 1 or more mercapto groups and 1 or more hydroxyl groups)

Examples of the thiol compound having a hydroxyl group include 2-mercaptoethanol, 3-mercapto-1, 2-propanediol, glycerol bis (mercaptoacetate), 4-mercaptophenol, 2, 3-dimercapto-1-propanol, pentaerythritol tris (3-mercaptopropionate), pentaerythritol tris (mercaptoacetate), and the like, but are not limited to these exemplified compounds.

(polyol Compound containing 2 or more hydroxyl groups)

The polyol compound may be 1 or more aliphatic or alicyclic alcohols. Specifically, examples thereof include linear or branched aliphatic alcohols, alicyclic alcohols, alcohols obtained by adding at least 1 selected from the group consisting of ethylene oxide, propylene oxide and epsilon-caprolactone to these alcohols, and the like. More specifically, there may be mentioned a compound exemplified in International publication No. 2016/125736.

The polyhydric alcohol compound is preferably at least 1 selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, 3-propanediol, 1, 2-cyclopentanediol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, and 1, 4-cyclohexanediol.

(amine Compound)

Examples of the amine compound include: ethylenediamine, 1, 2-or 1, 3-diaminopropane, 1,2-, 1, 3-or 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 10-diaminodecane, 1,2-, 1, 3-or 1, 4-diaminocyclohexane, o-, m-, p-diaminobenzene, 3, 4-or 4,4 '-diaminobenzophenone, 3, 4-or 4,4' -diaminodiphenyl ether, 4 '-diaminodiphenyl methane, 4' -diaminodiphenyl sulfide primary polyamine compounds such as 3,3 'or 4,4' -diaminodiphenyl sulfone, 2, 7-diaminofluorene, 1,5-, 1, 8-or 2, 3-diaminonaphthalene, 2,3-, 2, 6-or 3, 4-diaminopyridine, 2, 4-or 2, 6-diaminotoluene, m-xylylenediamine, isophoronediamine, diaminomethyl-bicycloheptane, 1, 3-or 1, 4-diaminomethyl-cyclohexane, 2-or 4-aminopiperidine, 2-or 4-aminomethylpiperidine, 2-or 4-aminoethylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, and the like;

Monofunctional secondary amine compounds such as diethylamine, dipropylamine, di-N-butylamine, di-sec-butylamine, diisobutylamine, di-N-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, methylhexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N-ethylaniline, dinaphthylamine, 1-methylpiperazine, morpholine;

n, N '-dimethylethylenediamine, N' -dimethyl-1, 2-diaminopropane, N '-dimethyl-1, 3-diaminopropane, N' -dimethyl-1, 2-diaminobutane, N '-dimethyl-1, 3-diaminobutane, N' -dimethyl-1, 4-diaminobutane, N, N '-dimethyl-1, 5-diaminopentane, N' -dimethyl-1, 6-diaminohexane, N '-dimethyl-1, 7-diaminoheptane, N' -diethyl ethylenediamine, N '-diethyl-1, 2-diaminopropane, N' -diethyl-1, 3-diaminopropane, N, N '-diethyl-1, 2-diaminobutane, N' -diethyl-1, 3-diaminobutane, N '-diethyl-1, 4-diaminobutane, N' -diethyl-1, 5-diaminopentane, N '-diethyl-1, 6-diaminohexane, N, N' -diethyl-1, 7-diaminoheptane, piperazine, 2-methylpiperazine, 2, 5-dimethylpiperazine, 2, 6-dimethylpiperazine, homopiperazine, 1-bis (4-piperidinyl) methane, 1, 2-bis (4-piperidinyl) ethane, 1, 3-bis (4-piperidinyl) propane, 1, 4-bis (4-piperidinyl) butane, secondary polyamine compounds such as tetramethylguanidine; etc.

Among the above, from the viewpoint of improving heat resistance and refractive index, the active hydrogen compound preferably contains a polythiol compound having 2 or more mercapto groups.

The content of the polythiol compound having 2 or more mercapto groups is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more, relative to the total mass of the active hydrogen compound.

In addition, as the active hydrogen compound in embodiment 1, the total content of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 8-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithioundecane, pentaerythritol tetrakis (3-mercaptopropionate) is preferably 60 mass% or more, more preferably 70 mass% or more, and further preferably 80 mass% or more, relative to the total mass of the active hydrogen compound.

In the composition, the molar ratio (NCO group/(OH group+sh group)) of the sum of hydroxyl groups (OH group) and mercapto groups (SH group) in the active hydrogen compound to the isocyanate groups (NCO group) in the isocyanate compound is preferably 0.8 or more, more preferably 0.85 or more, and still more preferably 0.9 or more.

In the composition, the molar ratio (NCO group/(OH group+sh group)) of the sum of hydroxyl groups (OH group) and mercapto groups (SH group) in the active hydrogen compound to the isocyanate groups (NCO group) in the isocyanate compound is preferably 1.2 or less, more preferably 1.15 or less, and still more preferably 1.1 or less.

Polymerization catalyst

The polymerizable composition for an optical material of embodiment 1 contains at least 1 polymerization catalyst.

The polymerization catalyst is not particularly limited, and for example, a basic catalyst, an organometallic catalyst, zinc carbamate, ammonium salt, sulfonic acid, and the like can be used.

The polymerization catalyst may be used in an amount of 1 or 2 or more kinds.

(alkaline catalyst)

Examples of the basic catalyst include amine-based catalysts (including imidazole-based catalysts).

Specific examples thereof include tertiary amine catalysts such as triethylenediamine, N-dimethylethanolamine, triethylamine and N-ethylmorpholine; 2-methylpyrazine, pyridine, α -methylpyridine, β -methylpyridine, γ -methylpyridine, 2, 6-dimethylpyridine, 3, 5-dimethylpyridine, 2,4, 6-trimethylpyridine, 3-chloropyridine, N-diethylaniline, N-dimethylaniline, hexamethylenetetramine, quinoline, isoquinoline, N-dimethyl-p-toluidine, N-dimethylpiperazine, quinaldine, 4-methylmorpholine, triallylamine, trioctylamine, 1, 2-dimethylimidazole, 1-benzyl-2-methylimidazole and the like.

Among the above, the amine-based catalyst is preferable as the basic catalyst.

Examples of the amine-based catalyst include 3, 5-lutidine; 2,4, 6-trimethylpyridine; tertiary amine catalysts such as triethylenediamine, N-dimethylethanolamine, triethylamine and N-ethylmorpholine; etc.

The amine-based catalyst preferably contains at least 1 selected from the group consisting of 3, 5-lutidine, 2,4, 6-collidine, triethylenediamine, N-dimethylethanolamine, and N-ethylmorpholine.

The basic catalyst also preferably contains a compound represented by the following general formula (2) and/or a compound represented by the following general formula (3).

[ chemical formula 2]

In the general formula (2), R ₁ Represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a halogen atom, and a plurality of R's are present ₁ May be the same or different. Q represents a carbon atom or a nitrogen atom. m represents an integer of 0 to 5.

[ chemical formula 3]

In the general formula (3), R ₂ 、R ₃ R is R ₄ Each independently represents a straight-chain alkyl group having 3 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an allyl group, or a hydrocarbon group containing a hydroxyl group.

The basic catalyst preferably has a pKa value of 1 or more, more preferably 3 or more, and still more preferably 4 or more.

The basic catalyst preferably has a pKa value of 9 or less, more preferably 8 or less.

The pKa value (acid dissociation index) can be measured, for example, by the method described in (a) The Journal of Physical Chemistry vol.68, number6, page1560 (1964), or (b) by the method using an automatic potential difference titration apparatus (AT-610 (trade name) manufactured by Kyoto electronic industries, inc.), or (c) by the acid dissociation index described in chemical review (modified 3 edition, showa 59, 25 th year, wash Co., ltd.) by the Japanese chemical society.

(organometallic catalyst)

Examples of the organometallic catalyst include organotin catalysts; organic acid salts of iron, nickel, zinc, etc.; an acetylacetone complex; a catalyst composition formed from a carboxylic acid metal compound and a quaternary ammonium salt compound; a catalyst composition formed from a 2-ring tertiary amine compound; metal catalysts in which alkoxy groups, carboxyl groups, and the like are coordinated to titanium or aluminum; etc.

Among the above, the organotin-based catalyst is preferable as the organometallic-based catalyst.

Examples of the organotin-based catalyst include dibutyltin Dichloride (DBC), dimethyltin Dichloride (DMC), dibutyltin dilaurate (DBTDL), dibutyltin diacetate, and the like.

The organotin-based catalyst preferably contains at least 1 selected from dibutyltin dichloride, dimethyltin dichloride, dibutyltin dilaurate and dibutyltin diacetate.

The polymerization catalyst preferably contains at least 1 selected from the group consisting of basic catalysts having pKa values of 4 to 8 and organometallic catalysts.

The polymerization catalyst also preferably contains at least 1 selected from the group consisting of amine-based catalysts and organotin-based catalysts.

The polymerization catalyst preferably contains at least 1 selected from the group consisting of 3, 5-lutidine, 2,4, 6-collidine, triethylenediamine, N-dimethylethanolamine, N-ethylmorpholine, dibutyltin dichloride, dimethyltin dichloride, dibutyltin dilaurate and dibutyltin diacetate.

In the polymerizable composition for an optical material according to embodiment 1, the content of the polymerization catalyst is more than 0.05 parts by mass and 2.0 parts by mass or less based on 100 parts by mass of the total of the 2 or more different monomers for an optical material.

The polymerization catalyst in embodiment 1 is contained in a larger amount than in the conventional method for producing an optical material.

Thus, in the curing step, when the monomer for an optical material in the polymerizable composition for an optical material is polymerized, the reaction heat of the polymerizable composition for an optical material (that is, the heat generated by self-heating) can be generated in a short time. Therefore, the polymerization reaction can be favorably promoted, as described later, the viscosity of the polymerizable composition can be increased, heat convection which is presumed to be a cause of the streak can be suppressed, and a high-quality optical material can be obtained in a shorter time than before.

The polymerization reaction can be favorably promoted by making the content of the polymerization catalyst larger than 0.05 parts by mass relative to 100 parts by mass of the total of the 2 or more different monomers for an optical material, and therefore, a high-quality optical material can be obtained in a short time. In addition, by favorably promoting the polymerization reaction, releasability at the time of taking out the cured product from the mold can be improved.

From the above viewpoint, the content of the polymerization catalyst is preferably 0.08 parts by mass or more, more preferably 0.10 parts by mass or more, still more preferably 0.13 parts by mass or more, and still more preferably 0.17 parts by mass or more, relative to 100 parts by mass of the total of the 2 or more different monomers for optical materials.

By setting the content of the polymerization catalyst to 2.0 parts by mass or less based on 100 parts by mass of the total of the 2 or more different monomers for an optical material, for example, the operability in injecting the polymerizable composition for an optical material into a mold can be improved.

From the above viewpoint, the content of the polymerization catalyst is preferably 1.8 parts by mass or less, more preferably 1.5 parts by mass or less, further preferably 1.0 parts by mass or less, particularly preferably 0.5 parts by mass or less, and still further preferably 0.3 parts by mass or less, relative to 100 parts by mass of the total of the 2 or more different monomers for optical materials.

The content of the polymerization catalyst may be appropriately set according to the type of the polymerization catalyst, the type and amount of the monomer (isocyanate compound, active hydrogen compound, other component, etc.) used, and the shape of the desired molded article.

The content range of the polymerization catalyst may be appropriately changed depending on the kind of the monomer for an optical material and the kind of the polymerization catalyst.

For example, when the monomer for an optical material contains dicyclohexylmethane diisocyanate and a mixture of 5, 7-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithioundecane and 4, 8-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithioundecane, and the polymerization catalyst contains 3, 5-dimethylpyridine, it is preferable to use 1.0 part by mass or more of the polymerization catalyst, and it is more preferable to use 1.5 parts by mass or more of the polymerization catalyst, relative to 100 parts by mass of the monomer for 2 or more different optical materials.

For example, when the monomer for an optical material contains 1, 3-bis (isocyanatomethyl) cyclohexane, pentaerythritol tetrakis (2-mercaptoacetate), and 2, 5-bis (mercaptomethyl) -1, 4-dithiane, and the polymerization catalyst contains 3, 5-lutidine, it is preferable to use 0.03 parts by mass or more of the polymerization catalyst, and more preferable to use 0.07 parts by mass or more of the polymerization catalyst, relative to 100 parts by mass of the monomer for 2 or more different optical materials.

The polymerization catalyst preferably satisfies the following condition 1.

[ condition 1]

Ea/R is-7100 or more and-2900 or less.

(Ea is the reaction rate constant of 2 or more different monomers for optical materials at 2 or more different temperatures, the activation energy calculated by an Arrhenius curve, and R is the gas constant (8.314J/mol/K))

By satisfying the condition 1, the polymerization catalyst can suppress the variation in polymerization rate during polymerization and curing of the polymerizable composition, and as a result, the occurrence of optical strain and striae can be suppressed, and an optical material excellent in appearance can be obtained.

The value of Ea was calculated by the following method.

The value of Ea was calculated by performing the following steps:

a physical property obtaining step of heating a composition 1 containing a polymerization-reactive compound and a predetermined amount of a polymerization catalyst to obtain a physical property value 1a from a functional group before heating of the polymerization-reactive compound and a physical property value 1b from a residual functional group after a predetermined time of heat preservation in the case of heat preservation at a plurality of temperatures;

a residual functional group ratio calculation step of calculating the residual functional group ratio 1 at a plurality of the temperatures from the physical property value 1a and the physical property value 1b;

a reaction rate constant calculation step of calculating reaction rate constants 1 at a plurality of temperatures based on the reaction rate formula from the residual functional group ratios 1;

Fitting, namely calculating the activation energy Ea1 and the frequency factor A1 by using an Arrhenius curve graph according to the reaction rate constants 1 at a plurality of temperatures.

Using the calculated Ea, it is determined whether the polymerization catalyst satisfies the condition 1.

The specific mode of the method for calculating Ea and the method for determining whether or not the polymerization catalyst satisfies the condition 1 is the same as the specific mode described in International publication No. 2020/256057.

(other additives)

The polymerizable composition for an optical material of embodiment 1 may contain an optional additive.

Examples of the optional additives include photochromic compounds, internal mold release agents, bluing agents, ultraviolet absorbers, and the like.

(photochromic Compounds)

The photochromic compound is a compound whose molecular structure changes reversibly by light irradiation of a specific wavelength, and whose light absorption characteristics (absorption spectrum) change in response to the change.

Examples of the photochromic compound used in embodiment 1 include a compound whose light absorption characteristics (absorption spectrum) change with respect to light of a specific wavelength.

In embodiment 1, the photochromic compound is not particularly limited, and any compound may be appropriately selected from conventionally known compounds usable for photochromic lenses. For example, 1 or 2 or more kinds of spiropyran compounds, spirooxazine compounds, fulgide compounds, naphthopyran compounds, bisimidazole compounds, and the like can be used depending on the desired coloring.

(internal Release agent)

The internal mold release agent may be an acidic phosphate. Examples of the acidic phosphate include phosphoric acid monoesters and phosphoric acid diesters, and the phosphoric acid monoesters and phosphoric acid diesters may be used alone or in combination of 2 or more kinds.

(bluing agent)

Examples of the bluing agent include a substance having an absorption band in a wavelength range from orange to yellow in a visible light region and a function of adjusting a hue of an optical material formed of a resin. More specifically, the bluing agent contains a substance that exhibits a blue to violet color.

(ultraviolet absorber)

Examples of usable ultraviolet absorbers include benzophenone-based ultraviolet absorbers such as 2,2' -dihydroxy-4-methoxybenzophenone, triazine-based ultraviolet absorbers such as 2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ]4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, benzotriazole-based ultraviolet absorbers such as 2- (2H-benzotriazol-2-yl) -4-methylphenol and 2- (2H-benzotriazol-2-yl) -4-tert-octylphenol, and benzotriazole-based ultraviolet absorbers such as 2- (2H-benzotriazol-2-yl) -4-tert-octylphenol and 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol. These ultraviolet absorbers may be used alone or in combination of 2 or more.

(viscosity)

From the viewpoint of suppressing striae, the polymerizable composition for an optical material of embodiment 1 has a viscosity of 10mpa·s or more, preferably 40mpa·s or more, more preferably 70mpa·s or more, still more preferably 80mpa·s or more, particularly preferably 100mpa·s or more, and still more preferably 120mpa·s or more, measured with a B-type viscometer at 25 ℃ and 60 rpm.

In the polymerizable composition for an optical material according to embodiment 1, the viscosity of the composition measured by a B-type viscometer at 25 ℃ and 60rpm is 1000mpa·s or less, preferably 700mpa·s or less, and more preferably 400mpa·s or less, from the viewpoint of maintaining the operability of molding the optical material into a desired shape.

The viscosity of the polymerizable composition for an optical material according to embodiment 1 can be adjusted according to the application of the cured product obtained.

For example, in the case of obtaining a cured product using a mold for a convex lens (plus lenses), the end face (i.e., injection port) is narrow (for example, 1mm to 3 mm), and therefore, in the polymerizable composition for an optical material of embodiment 1, the viscosity is preferably 10mpa·s to 100mpa·s from the viewpoint of suppressing striae.

On the other hand, in the case where a cured product is obtained using a mold for a normal lens other than a convex lens, the end face (i.e., the injection port) is wide (for example, 5mm to 15 mm), and therefore, in the polymerizable composition for an optical material of embodiment 1, the viscosity is preferably 10mpa·s to 1000mpa·s, and more preferably 100mpa·s to 1000mpa·s, from the viewpoint of suppressing striae.

By increasing the viscosity of the polymerizable composition for an optical material, when the composition is heated from the outside, thermal convection due to a temperature difference between the inside and the outside of the composition can be suppressed, and the occurrence of striae due to thermal convection can be reduced.

However, since the rate of adhesion at the time of polymerization is insufficient when the amount of the catalyst is small, the maximum temperature difference does not increase to such an extent that heat convection can be suppressed, and the temperature cannot be rapidly increased in a short time. In addition, the time required until the polymerization is completed becomes long.

On the other hand, according to the present disclosure, the catalyst amount is increased to the most suitable range in consideration of the reactivity of the isocyanate compound having no aromatic ring, whereby the viscosity of the entire composition can be more rapidly increased. This suppresses the uneven polymerization and also suppresses the heat convection due to the rapid temperature rise, thereby enabling the polymerization to be performed in a short time.

(thixotropic ratio)

The thixotropic ratio of the polymerizable composition for an optical material according to embodiment 1 is preferably 1.3 or less, more preferably 1.2 or less, and further preferably 1.1 or less.

By setting the thixotropic ratio of the polymerizable composition for an optical material of embodiment 1 to 1.3 or less, the composition can be rapidly filled into a polymerization vessel such as a mold described later, and heat convection during polymerization can be suppressed, thereby further preventing occurrence of striae and the like in the monomer for an optical material. As a result, the occurrence of striae and the like can be suppressed in the obtained optical material, and the quality can be maintained well.

The thixotropic ratio of the polymerizable composition for an optical material according to embodiment 1 is preferably 0.9 or more, more preferably 0.95 or more, and further preferably 1.0 or more.

The thixotropic ratio can be determined by the viscosity eta using a B-type viscometer at 25℃and a rotation speed of 6rpm ₁ Divided by the viscosity eta measured at a speed of 60rpm ₂ To calculate.

For example, the thixotropic ratio can be reduced by reducing the molecular weight of 2 or more monomers for optical materials, suppressing the polymerization degree of the prepolymer to a certain value or less, or reducing the ratio of structures providing elasticity in the monomers.

The polymerizable composition for an optical material of embodiment 1 preferably comprises: 2 or more different monomers for optical materials; a polymerization catalyst; and a prepolymer having a polymerizable functional group, wherein the prepolymer is a polymer of 2 or more different monomers for an optical material.

The prepolymer is a polymer of 2 or more different monomers for optical materials, and is a polymer having a polymerizable functional group.

A cured product obtained by polymerizing a prepolymer with 2 or more different monomers for optical materials can be used as an optical material.

Examples of the prepolymer include: a polymer in which 2 kinds of polymerizable functional groups of the monomers for optical materials are not polymerized at an equivalent ratio of 1:1; and a polymer obtained by polymerizing 2 kinds of monomers for optical material among the monomers for optical material at an unbalanced equivalent ratio.

The polymerizable functional group is a functional group polymerizable with other polymerizable functional groups, and specifically, an active hydrogen-containing functional group such as an isocyanate group or a mercapto group described later is exemplified.

The polymerization carried out at an equivalent ratio of 1:1 means, for example: when the polymerization is carried out using an isocyanate compound and a polythiol compound, the polymerization is carried out in such an amount that the molar ratio of the isocyanate group of the isocyanate compound to the mercapto group of the polythiol compound becomes 1:1.

Polymerizable prepolymer composition for optical Material

The polymerizable prepolymer composition for optical materials according to embodiment 1 comprises: a prepolymer having a polymerizable functional group, the prepolymer being a polymer of 2 or more different monomers for an optical material; and a polymerization catalyst, wherein at least 1 of the 2 or more different monomers for an optical material is an isocyanate compound having no aromatic ring, and the viscosity of the polymerizable prepolymer composition for an optical material is 10 mPas to 2000 mPas measured by a B-type viscometer at 25 ℃ and 60 rpm.

It is preferable that the viscosity of the prepolymer composition is not easily changed (i.e., stabilized) with the lapse of time. For example, the polymerizable prepolymer composition for optical materials preferably does not contain a component having another polymerizable functional group that is easily polymerized with the polymerizable functional group contained in the prepolymer described later.

The term "stable viscosity of the prepolymer composition" means that the prepolymer composition has a viscosity change of 10% or less before and after storage at 20℃for 24 hours.

The specific examples, preferred modes, and the like of the monomer for an optical material and the polymerization catalyst of the polymerizable prepolymer composition for an optical material are the same as those described in the above item of the polymerizable composition for an optical material.

The definition of the prepolymer of the polymerizable prepolymer composition for optical materials is the same as the definition of the prepolymer described in the item of the polymerizable composition for optical materials.

The specific examples, preferred modes, and the like of the isocyanate compound having no aromatic ring and the viscosity contained as the monomer for an optical material in the polymerizable prepolymer composition for an optical material are the same as those described in the above item of the polymerizable composition for an optical material.

The content of the polymerization catalyst in the polymerizable prepolymer composition for an optical material according to embodiment 1 is preferably 0.1 to 4.0 parts by mass based on 100 parts by mass of the total of the 2 or more different monomers for an optical material.

The polymerization reaction can be favorably promoted by setting the content of the polymerization catalyst to 0.1 part by mass or more based on 100 parts by mass of the total of the 2 or more different monomers for optical materials, and therefore, a high-quality optical material can be obtained in a short time. In addition, by favorably promoting the polymerization reaction, releasability at the time of taking out the cured product from the mold can be improved.

From the above viewpoints, the content of the polymerization catalyst is preferably 0.15 parts by mass or more, more preferably 0.20 parts by mass or more, relative to 100 parts by mass of the total of the 2 or more different monomers for optical materials.

By setting the content of the polymerization catalyst to 4.0 parts by mass or less based on 100 parts by mass of the total of the 2 or more different monomers for an optical material, for example, the operability in injecting the polymerizable composition for an optical material into a mold can be improved.

From the above viewpoint, the content of the polymerization catalyst is preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, and still more preferably 1.0 part by mass or less, based on 100 parts by mass of the total of the 2 or more different monomers for optical materials.

(thixotropic ratio)

The thixotropic ratio of the polymerizable prepolymer composition for an optical material according to embodiment 1 is preferably 1.3 or less, more preferably 1.2 or less, and further preferably 1.1 or less.

By setting the thixotropic ratio of the polymerizable prepolymer composition for optical materials according to embodiment 1 to 1.3 or less, the composition can be rapidly filled into a polymerization vessel such as a mold described later, and heat convection during polymerization can be suppressed, thereby further preventing occurrence of striae and the like in the monomer for optical materials. As a result, the occurrence of striae and the like can be suppressed in the obtained optical material, and the quality can be maintained well.

The thixotropic ratio was determined as described above.

In the polymerizable prepolymer composition for optical materials according to embodiment 1, it is sometimes preferable that the prepolymer contain isocyanate groups from the viewpoint of the handleability of the composition.

That is, it is preferable that not all the isocyanate groups of the prepolymer are polymerized, but only a part of the isocyanate groups are polymerized, and 85% or more of the isocyanate groups of the isocyanate compound used for producing the prepolymer composition remain without polymerization.

By containing the isocyanate group in the prepolymer, that is, by containing the isocyanate compound in a larger amount than the other monomer for optical material that can be polymerized with the isocyanate compound, the viscosity of the polymerizable prepolymer composition for optical material can be kept low when the viscosity of the other monomer for optical material is high, and handling of the composition is facilitated.

The polymerizable prepolymer composition for optical materials according to embodiment 1 preferably further contains substantially no isocyanate groups in the prepolymer.

The term "prepolymer substantially does not contain isocyanate groups" means a state in which substantially all of the isocyanate groups are polymerized.

Specifically, the phrase "the prepolymer does not substantially contain isocyanate groups" means that the content of isocyanate groups in the prepolymer is not more than the detection limit when measured by an IR spectrometer.

Since the prepolymer does not substantially contain isocyanate groups, there is substantially no isocyanate group having high reactivity, and therefore, the stability of the polymerizable prepolymer composition for optical materials can be improved.

The polymerizable prepolymer composition for optical materials according to embodiment 1 is preferably one in which the refractive index B of the prepolymer raw material composition (which is a composition before formation of a prepolymer and contains the aforementioned 2 or more different monomers for optical materials and a polymerization catalyst) is subtracted from the refractive index a of the polymerizable prepolymer composition for optical materials (also referred to as "refractive index a-refractive index B") to obtain a value of preferably greater than 0, more preferably 0.003 or more, and even more preferably 0.010 or more.

The refractive index a is the refractive index of the polymerizable prepolymer composition for optical material after polymerizing the monomer for optical material with the polymerization catalyst to obtain the prepolymer, and the refractive index B is the refractive index of the prepolymer raw material composition before polymerizing the monomer for optical material with the polymerization catalyst to obtain the prepolymer.

When the refractive index a-refractive index B is within the above range, the polymerizable composition for an optical material can be easily adjusted to a predetermined viscosity. In addition, the quality (for example, refractive index, appearance, etc.) of the cured product of the polymerizable composition for optical materials can be easily stabilized.

The refractive index a-refractive index B may be 0.020 or less, or 0.018 or less.

When the prepolymer contains isocyanate groups, the refractive index a-refractive index B is preferably 0.005 or more, more preferably 0.010 or more. Further, it is preferably 0.030 or less, more preferably 0.020 or less.

On the other hand, when the prepolymer contains substantially no isocyanate groups, the refractive index a-refractive index B is preferably 0.003 or more, more preferably 0.005 or more. Further, it is preferably 0.020 or less, more preferably 0.015 or less.

Cured product

The cured product of embodiment 1 is the polymerizable composition for an optical material of embodiment 1 or the cured product of the polymerizable prepolymer composition for an optical material of embodiment 1.

In the cured product of embodiment 1, the content of amine is preferably 0.03 mass% or more, more preferably 0.05 mass% or more, and even more preferably 0.07 mass% or more, when an amine-based catalyst is used as a polymerization catalyst from the viewpoint of reducing the striae.

In addition, the content of the amine in the cured product of embodiment 1 is preferably 2.5 mass% or less, more preferably 2.0 mass% or less, and even more preferably 1.5 mass% or less, from the viewpoint of improving the handleability of the polymerizable composition for an optical material.

The amine content is an amine content measured by gas chromatography mass spectrometry from a methylene chloride composition obtained by dispersing a cured product in methylene chloride and performing ultrasonic extraction.

In the cured product of embodiment 1, the content of tin is preferably 0.05 mass% or more, more preferably 0.1 mass% or more, and even more preferably 0.2 mass% or more, when an organotin-based catalyst is used from the viewpoint of reducing striae.

In addition, the content of tin in the cured product of embodiment 1 is preferably 2.5 mass% or less, more preferably 2.0 mass% or less, and even more preferably 1.5 mass% or less, from the viewpoint of improving the handleability of the polymerizable composition for an optical material.

The method for measuring the amine content in the cured product is as follows.

200mg of the solidified material formed into a powder by filing and 3mL of methylene chloride were placed in a centrifuge tube (volume: 10 mL), and ultrasonic extraction was performed at room temperature for 10 minutes using an ultrasonic washer (manufactured by IUCHI Co., ltd., US-4), and centrifugal separation was performed at 4000rpm for 10 minutes using a centrifugal separator (manufactured by KUBIOTA Co., ltd., bench-top small-sized centrifuge 2410).

The supernatant was collected, and the residue was dispersed again in 3mL of methylene chloride, followed by the above-mentioned ultrasonic extraction and centrifugal separation, and the supernatant was collected (hereinafter also referred to as "residue extraction").

After the residue was further extracted 2 times, methylene chloride was added to the obtained supernatant to make the total amount 10mL.

10mL of the obtained supernatant was filtered and analyzed by gas chromatography-mass spectrometry (also referred to as GC-MS.) (GC-MS apparatus: manufactured by Agilent Co., ltd., 6890GC/5973N MSD, column: CP-Sil 8CB for Amine (0.25 mmID. Times.30 mF.T=0.25 μm)), to obtain a peak area value derived from Amine. The peak area value derived from the amine and the standard curve of the amine amount were prepared, and the amine content in the cured product was measured.

The amine refers to an amine compound that can be used as a polymerization catalyst or an amine compound derived from the amine compound.

In particular, in the optical application requiring light transmittance, the cured product of embodiment 1 preferably has a devitrification degree of less than 50, more preferably less than 35.

Devitrification can be measured by the following method.

Light from a light source (e.g., HAYASHI-REPIC co., ltd. Luminear Ace LA-150A) is transmitted through the cured product in the dark. An image of light transmitted from the cured product is collected in an image processing apparatus (for example, an image processing apparatus manufactured by Ube Information Systems inc.) and the collected image is subjected to shading, the shading degree of the processed image is digitized for each pixel, and a value calculated as an average value of the values of the shading degree of each pixel is regarded as a devitrification degree.

The cured product of embodiment 1 preferably has no cord of a length of 1.0mm or more in a range of 15mm in radius from the center of the cured product, and more preferably has no cord of a length of 1.0mm or more in and out of a range of 15mm in radius from the center of the cured product.

More specifically, the cured product of embodiment 1 may be a cured product of 2 or more different optical monomers, wherein at least 1 of the 2 or more different optical monomers is an isocyanate compound having no aromatic ring, no streaks having a length of 1.0mm or more are present within a radius of 15mm from the center of the cured product, and the amine content is 0.03 mass% or more and 2.5 mass% or less as measured by gas chromatography mass spectrometry.

The above-mentioned 2 or more different optical monomers and isocyanate compounds having no aromatic ring are mentioned.

In the cured product of the present disclosure, 2 or more different optical monomers may include an isocyanate compound other than an isocyanate compound having no aromatic ring.

When the 2 or more different optical monomers include an isocyanate compound having no aromatic ring and an isocyanate compound having an aromatic ring, the ratio of the isocyanate compound having no aromatic ring to the isocyanate compound having an aromatic ring is preferably in the range of 7:3 to 10:0, more preferably in the range of 8:2 to 10:0, in terms of the molar ratio of isocyanate groups, from the viewpoint of controlling the polymerization reaction.

Method for producing optical Material

The method for producing an optical material according to embodiment 1 includes the following methods a and B.

< preparation A >

The preparation method A comprises the following steps:

a preparation step of preparing a polymerizable composition for an optical material, the polymerizable composition for an optical material containing 2 or more different monomers for an optical material; and a polymerization catalyst, wherein at least 1 of the 2 or more different optical material monomers is an isocyanate compound having no aromatic ring, and the content of the polymerization catalyst is more than 0.05 parts by mass and 2.0 parts by mass or less relative to 100 parts by mass of the total of the 2 or more different optical material monomers;

a casting step of adjusting the viscosity of the polymerizable composition for an optical material to 10 to 1000 mPas measured by a B-type viscometer at 25 ℃ and 60rpm, and casting the composition into a mold; and

and a curing step of curing the polymerizable composition for an optical material by polymerizing the 2 or more different monomers for an optical material in the polymerizable composition for an optical material in the mold.

The preparation method a includes the preparation step, the viscosity adjustment step, and the curing step, so that the quality of the obtained optical material can be maintained and the production time of the optical material can be shortened.

The preparation method a may include the preparation step, the viscosity adjustment step, and the curing step in this order.

The content of the polymerization catalyst in the polymerizable composition for optical materials prepared in the preparation step in the production method a is more than 0.05 parts by mass and 2.0 parts by mass or less based on 100 parts by mass of the total of the 2 or more different monomers for optical materials. The content of the polymerization catalyst is larger than that of the conventional method for producing an optical material.

Thus, in the curing step, when the monomer for an optical material in the polymerizable composition for an optical material is polymerized, the reaction heat of the polymerizable composition for an optical material (that is, the heat generated by self-heating) can be generated in a short time.

The polymerization reaction of the monomer for an optical material in the polymerizable composition for an optical material can be accelerated by the reaction heat, and therefore, a high-quality optical material can be obtained in a shorter time than before.

Conventionally, when the polymerization reaction is carried out, the polymerizable composition for an optical material is mainly heated to cause the polymerization reaction to occur, but in the production method a, the heating of the polymerizable composition for an optical material is not necessarily required.

In addition, since the self-heating of the composition is also utilized in the production method a, polymerization can be performed without excessively depending on the heat supplied from the outside, and therefore, not only the viscosity of the composition to be described later can be increased, but also the heat unevenness and heat convection in the polymerizable composition for an optical material can be suppressed, and the occurrence of striae can be suppressed.

In the present disclosure, the "rib" refers to a state in which the refractive index of a specific portion is different from the normal refractive index of the surrounding portion. In addition, it may also be shown that a disadvantageous state occurs in the intended use of the optical material. In optical materials, the striae are a defect.

< preparation procedure >

The preparation method A comprises the following steps:

a preparation step of preparing a polymerizable composition for an optical material, the polymerizable composition for an optical material containing 2 or more different monomers for an optical material; and a polymerization catalyst, wherein at least 1 of the 2 or more different optical material monomers is an isocyanate compound having no aromatic ring, and the content of the polymerization catalyst is more than 0.05 parts by mass and 2.0 parts by mass or less relative to 100 parts by mass of the total of the 2 or more different optical material monomers.

The preparation step may be a step of simply preparing a prefabricated polymerizable composition for an optical material, or may be a step of manufacturing a polymerizable composition for an optical material.

The polymerizable composition for optical materials in the preparation step is not particularly limited as long as it contains 2 or more different monomers for optical materials and a polymerization catalyst.

As the polymerizable composition for optical materials, a ready-made product may be used, or at least 2 or more different monomers for optical materials and a polymerization catalyst may be mixed and prepared.

The method of mixing is not particularly limited, and known methods can be used.

The temperature at which the above components are mixed is not particularly limited, but is preferably 30℃or less, and more preferably room temperature (25 ℃) or less.

From the viewpoint of the pot life of the prepared polymerizable composition for an optical material, it is sometimes preferable to set the temperature to be lower than 25 ℃. However, in the case where the solubility of the additives such as the internal mold release agent and the above-mentioned components is poor, the above-mentioned components may be heated in advance to dissolve the above-mentioned additives in the above-mentioned components.

When the above components are mixed, it is preferable to dry the polymerizable composition for an optical material under an inert gas in order to prevent the mixing of moisture.

The preparation step is preferably a step of mixing the polymerization catalyst in advance in a part of the 2 or more different monomers for optical materials, and then further mixing the rest of the 2 or more different monomers for optical materials, thereby producing the polymerizable composition for optical materials.

This prevents polymerization of a part of the 2 or more different optical material monomers and the remainder of the 2 or more different optical material monomers from occurring before a mixture including a part of the 2 or more different optical material monomers and the polymerization catalyst is mixed with a mixture including no polymerization catalyst and the remainder of the 2 or more different optical material monomers.

Therefore, by performing the preparation step in the above-described order, the start timing of polymerization can be adjusted. Therefore, for example, the operability when the polymerizable composition for an optical material is injected into a mold can be improved.

In the preparation step, the polymerization catalyst may be mixed in advance in a part of the 2 or more different monomers for optical materials, and then the mixture may be mixed singly or the remainder of the 2 or more different monomers for optical materials may be mixed in a plurality of times.

Specific examples of the preparation step include the following.

First, a part of the monomer for optical material and an additive (for example, an internal mold release agent) are charged to prepare a mixed solution. The mixture was stirred at 25℃for 1 hour to dissolve the components completely, and then a part of the remainder of the monomer for optical material was further charged and stirred to prepare a homogeneous solution. The solution was deaerated to obtain a 1 st mixed solution.

Next, the remaining part of the monomer for optical material and the catalyst were stirred at 25 ℃ for 30 minutes to be completely dissolved, thereby obtaining a 2 nd mixed solution.

Then, the 1 st mixed solution and the 2 nd mixed solution were mixed to obtain a uniform solution, thereby obtaining a polymerizable composition for an optical material.

< casting procedure >)

The production method B comprises a casting step of adjusting the viscosity of the polymerizable composition for optical materials to 10 mPas to 1000 mPas as measured by a B-type viscometer at 25 ℃ and 60rpm, and casting the composition into a mold.

By adjusting the viscosity of the polymerizable composition for an optical material to the above range and casting, the viscosity of the polymerizable composition for an optical material produced in the step of producing the polymerizable composition for an optical material can be made to be within an appropriate range from the viewpoint of suppressing the striae in the obtained optical material.

From the above viewpoints, the viscosity of the polymerizable composition for an optical material is 10mpa·s or more, preferably 40mpa·s or more, more preferably 70mpa·s or more, further preferably 80mpa·s or more, particularly preferably 100mpa·s or more, further preferably 120mpa·s or more.

From the viewpoint of maintaining good handleability when molding an optical material into a desired shape, the viscosity of the polymerizable composition for an optical material is 1000mpa·s or less, preferably 700mpa·s or less, and more preferably 400mpa·s or less.

The method for adjusting the viscosity of the polymerizable composition for optical materials is not particularly limited.

For example, the viscosity of the polymerizable composition for an optical material can be adjusted by adding a high-viscosity compound, heating, stirring, or the like.

< curing Process >)

The preparation method A comprises the following steps:

The method a can produce an optical material by polymerizing the polymerizable composition for an optical material by including a curing step.

Conventionally, when the polymerization reaction is performed, the polymerizable composition for an optical material is heated to cause the polymerization reaction, but the polymerizable composition for an optical material in the production method a can promote the polymerization reaction of the monomer for an optical material in the polymerizable composition for an optical material by increasing the reaction heat associated with the polymerization reaction (i.e., heat generated by self-heating).

Therefore, in the production method a, heating of the polymerizable composition for an optical material is not necessarily required, but heating may be performed.

That is, in the curing step of the production method a, the polymerizable composition for an optical material is allowed to stand, whereby the polymerizable composition for an optical material can be cured by polymerization.

The environment in which the curing step is performed is not particularly limited, and the curing may be performed by heating the mold from the outside of the mold, but from the viewpoint of improving the optical quality such as the striae and polymerizing in a short time, it is preferable that the polymerizable composition for an optical material is allowed to stand in a closed space, thereby curing the polymerizable composition for an optical material.

By allowing the polymerizable composition for an optical material to stand in the closed space, heat generated by self-heating of the polymerizable composition for an optical material can be prevented from being released to the outside. This can retain heat generated by self-heating in the closed space, and thus can promote the polymerization reaction more efficiently, and can produce an optical material in a shorter time.

Examples of the closed space include a heat-insulating environment.

The heat-insulating environment is an environment in which heat is kept inside and heat conduction between the inside and the outside is suppressed. The environment in which heat conduction between the inside and the outside is suppressed means the following environment: when the polymerizable composition for an optical material is left to stand in the closed space, the heat conductivity between the inside and the outside of the closed space is such that the polymerizable composition for an optical material can be cured.

The insulating environment may be formed using an insulating material, for example.

That is, by allowing the polymerizable composition for an optical material to stand in the heat insulating container formed of the heat insulating material, heat can be held in the heat insulating container, and heat conduction between the inside and the outside can be suppressed.

The thermal conductivity of the heat insulating material is preferably 0.50W/mK or less, more preferably 0.10W/mK or less, and still more preferably 0.05W/mK or less.

The density of the insulating material is preferably 10kg/m ³ The above is more preferably 15kg/m ³ The above is more preferably 20kg/m ³ The above.

In the "heat-insulating" or "heat-insulating environment" in the production method a, it is preferable that the heating for bringing the heat-insulating reaction vessel into a constant temperature state (constant temperature reaction vessel) is performed within a range that does not interfere with the polymerization reaction based on the reaction heat of the polymerizable composition for optical materials or excessively promote the polymerization reaction of the polymerizable composition for optical materials due to the heating from the outside.

Thus, the ambient temperature in the reaction vessel (constant temperature reaction vessel) in which the mold is placed can be set to a heat-retaining state or a constant temperature state according to a temperature rise state or the like caused by self-heating of the optical material monomer, and thus, the polymerization reaction can be more favorably promoted.

As the heat-insulating environment, for example, the heat-insulating reaction tank or the constant temperature reaction tank described above can be used.

For example, when a mold filled with a monomer is left to stand in a vacuum vessel as a heat-insulating reaction vessel, heat-insulating polymerization in a heat-insulating environment using a heat-insulating reaction vessel (constant temperature reaction vessel) can be performed in accordance with the following procedure.

The inner surface of the vacuum vessel is covered with a member having heat insulating property and heat preserving property such as urethane foam or cork, and the mold filled with the monomer is covered with a member such as cloth as necessary. Then, the mold filled with the monomer is allowed to stand in the vacuum vessel.

The curing step may be a step of curing the polymerizable composition for an optical material by allowing the polymerizable composition for an optical material to stand without heating from the outside.

As described above, in the method a, heating of the polymerizable composition for optical material is not necessary.

For heating from the outside, a device may be used, and the economic burden may be increased. In the case of the method A, the optical material can be produced by a simple method, and thus the economic burden can be reduced.

The curing step is preferably a step of allowing the polymerizable composition for an optical material to stand for 2 to 10 hours, thereby curing the polymerizable composition for an optical material.

According to the conventional method, the polymerization reaction is usually carried out over several hours to several tens of hours (for example, about 20 hours to 48 hours) while gradually increasing the temperature by heating.

When the polymerization reaction time is short, the polymerizable composition for optical materials does not cure completely, and therefore, optical materials cannot be obtained or the quality of optical materials is degraded.

However, by the production method a, the optical material can be produced in a short time while maintaining the quality of the obtained optical material. Specifically, the polymerizable composition for an optical material can be allowed to stand for 10 hours or less to produce an optical material.

From the above point of view, in the curing step, it is more preferable that the polymerizable composition for an optical material is allowed to stand for 8 hours or less.

In addition, from the viewpoint of obtaining an optical material after polymerization reaction and good curing, the polymerizable composition for an optical material is preferably left to stand for 2 hours or more, more preferably 5 hours or more.

In the curing step, a microwave irradiation step of irradiating the polymerizable composition for an optical material with microwaves for a predetermined time may be provided, if necessary.

One embodiment of the curing step includes the following steps a and b.

Step a: the polymerizable composition for an optical material is injected (cast) into a mold (into a cavity of a mold).

Step b: the mold filled with the polymerizable composition for optical material is allowed to stand in a closed space for a predetermined period of time, and heat-insulating polymerization is performed.

(Process a)

First, a polymerizable composition is injected into a molding die (mold) held by a gasket, an adhesive tape, or the like. In this case, it is preferable to perform, as necessary, a defoaming treatment under reduced pressure, a filtration treatment under increased pressure, a filtration treatment under reduced pressure, or the like, depending on the physical properties required for the obtained optical material.

(Process b)

The polymerization conditions are not limited, and are preferably appropriately adjusted according to the composition of the polymerizable composition for optical material, the kind and amount of the catalyst, the shape of the mold, and the like.

The mold filled with the polymerizable composition for optical material may be allowed to stand for 2 to 4 hours in an insulating environment to polymerize.

In the step b, a heating step may be added after the heat-insulating polymerization step of allowing the mold filled with the polymerizable composition for an optical material to stand for a certain period of time in a heat-insulating environment, if necessary.

In the step b, the mold into which the polymerizable composition for an optical material is injected may be heated, or the inside of the heat-insulating reaction tank may be heated, in parallel with the step of allowing the mold into which the polymerizable composition for an optical material is injected to stand in a heat-insulating environment (heat-insulating polymerization), continuously or intermittently at a temperature not higher than the self-heating temperature generated by the polymerizable composition for an optical material in the heat-insulating polymerization process, or the inside of the heat-insulating reaction tank may be heated, thereby keeping the ambient temperature in the heat-insulating reaction tank.

< annealing Process >)

If necessary, the method A may include an annealing step of annealing the cured polymerizable composition for optical materials.

The annealing treatment is usually performed at a temperature of 50 to 150 ℃, preferably 90 to 140 ℃, and more preferably 100 to 130 ℃.

< other procedures >

Other steps may be provided for the recipe a as needed.

As another step, for example, in the case of producing an optical material using a mold, an injection step of injecting a polymerizable composition for an optical material into the mold is exemplified.

< use of optical Material >

The optical material in the manufacturing method a can be used for plastic lenses, prisms, optical fibers, information recording substrates, filters, light emitting diodes, and the like.

Among the above, the optical material in embodiment 1 can be suitably used for a plastic lens, and can be more suitably used for a plastic lens for spectacles.

< preparation method B >)

The preparation method B comprises the following steps:

a prepolymer step of mixing a part of the 2 or more different monomers for optical materials with at least a part of the polymerization catalyst, and polymerizing at least a part of the 2 or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer;

The preparation method B includes a preparation step and a prepolymer processing step, whereby the striae in the obtained optical material can be suppressed and the manufacturing time of the optical material can be shortened.

The preparation method B preferably includes the following steps in addition to the preparation step and the prepolymer step:

The production method B can further preferably suppress the striae in the obtained optical material and can further preferably shorten the production time of the optical material by including the step of producing the polymerizable composition for optical material and the curing step in addition to the preparation step and the prepolymer step.

The polymerizable composition for optical materials prepared in the preparation step in the production method B has a content of the polymerization catalyst of 0.010 to 2.0 parts by mass based on 100 parts by mass of the total of 2 or more different monomers for optical materials. As in the case of the production method a, the content of the polymerization catalyst is larger than in the case of the conventional method for producing an optical material.

Therefore, as in the case of the production method a, a high-quality optical material with suppressed striae can be obtained in a shorter time than in the conventional case.

In the same manner as in the case of the method A, in the method B, heating of the polymerizable composition for optical material is not necessary.

In addition, the production method B includes a preparation step, a prepolymer processing step, a step of producing a polymerizable composition for an optical material, and a curing step, whereby convection in a mold in which a polymerization reaction is performed can be suppressed, and occurrence of striae in the obtained cured product can be suppressed.

In addition, by including the prepolymer process in the production method B, the storage stability of the mixture containing the prepolymer (for example, the polymerizable composition for an optical material) can be maintained more favorably than in the case where the prepolymer process is not accompanied.

For example, when the mixture containing the prepolymer is stored for a certain period of time, the polymerization reaction in the mixture can be suppressed. I.e. a longer shelf life can be ensured.

< preparation procedure >

The preparation method B comprises the following steps: a preparation step of preparing a total of 100 parts by mass of 2 or more different monomers for optical materials and 0.010 to 2.0 parts by mass of a polymerization catalyst.

In the preparation step, a total of 100 parts by mass of 2 or more different monomers for optical materials and 0.010 to 2.0 parts by mass of a polymerization catalyst are prepared.

That is, for the production method B, 0.010 to 2.0 parts by mass of the polymerization catalyst is used per 100 parts by mass of the total of 2 or more different monomers for optical materials.

By using 0.010 parts by mass or more of the polymerization catalyst per 100 parts by mass of the 2 or more different monomers for optical materials, the polymerization reaction can be favorably promoted, and therefore, a high-quality optical material with the striae suppressed can be obtained in a short time. In addition, by favorably promoting the polymerization reaction, releasability at the time of taking out the cured product from the mold can be improved.

From the above point of view, the polymerization catalyst is preferably used in an amount of 0.015 parts by mass or more, more preferably 0.038 parts by mass or more, still more preferably 0.10 parts by mass or more, and particularly preferably 0.17 parts by mass or more, based on 100 parts by mass of 2 or more different monomers for optical materials.

For example, when the monomer for an optical material contains 2,5 (6) -bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane, pentaerythritol tetrakis (3-mercaptopropionate), and 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, and the polymerization catalyst contains 3, 5-dimethylpyridine, the polymerization catalyst is preferably used in an amount of 0.10 parts by mass or more, more preferably 0.17 parts by mass or more, relative to 100 parts by mass of the monomer for 2 or more different optical materials.

By using 2.0 parts by mass or less of the polymerization catalyst per 100 parts by mass of the 2 or more different monomers for optical materials, for example, the operability in injecting the polymerizable composition for optical materials into a mold can be improved.

From the above viewpoints, it is preferable to use 1.5 parts by mass or less of the polymerization catalyst per 100 parts by mass of the monomer for 2 or more different optical materials.

Depending on the type of the monomer for optical material and the type of the polymerization catalyst, the polymerization catalyst may be used in an amount of 1.0 part by mass or less, 0.3 parts by mass or less, or 0.15 parts by mass or less based on 100 parts by mass of 2 or more different monomers for optical material.

The amount of the polymerization catalyst may be appropriately set according to the type of the polymerization catalyst, the type and amount of the monomer (isocyanate compound, active hydrogen compound, other component, etc.) used, and the shape of the desired molded article.

< prepolymer procedure >)

The preparation method B comprises the following steps:

and a prepolymer step of mixing at least a part of the 2 or more different monomers for optical materials with at least a part of the polymerization catalyst, and polymerizing at least a part of the 2 or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer.

The inventors of the present application considered that convection occurs due to uneven temperature distribution in a mold in which polymerization reaction is performed, which is one of the causes of occurrence of streaks in the obtained cured product.

Accordingly, the inventors of the present application focused on producing a prepolymer by polymerizing a part of a monomer for an optical material in advance, and increasing the viscosity of the polymerizable composition for an optical material by including the prepolymer in the polymerizable composition for an optical material. Thereby, convection in the mold can be suppressed.

In addition, in the production method B, the self-heating is prevented from escaping to the outside, and thus the temperature difference between the inside and the outside of the mold is less likely to occur.

From the above viewpoints, it is presumed that the method B can suppress the streaks of the obtained cured product.

The production method B can obtain a prepolymer excellent in pot life by including all of 1 kind of optical material monomer among 2 or more kinds of different optical material monomers, a part of the other optical material monomers other than the 1 kind of optical material monomer, and all or a part of the polymerization catalyst in the prepolymer process.

The mode of "part of 2 or more different monomers for optical materials" is not particularly limited.

For example, "a part of the 2 or more different monomers for optical materials" may be an amount of a part of each of the 2 or more different monomers for optical materials.

The "part of the 2 or more different optical material monomers" may be all of 1 or more optical material monomers among the 2 or more different optical material monomers.

In the prepolymer step, a part of the polymerization catalyst may be used, or the whole may be used.

When a part is used as the polymerization catalyst, the mode of "a part of the polymerization catalyst" is not particularly limited, as in "a part of 2 or more different monomers for optical materials".

For example, a "portion of a polymerization catalyst" may be an amount of a portion of a polymerization catalyst.

When a part is used as the polymerization catalyst, from the viewpoint of securing a long-term storage life, the part of the polymerization catalyst is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 15 to 50 parts by mass, out of 100 parts by mass of the polymerization catalyst.

From the viewpoint of securing a long-term storage life, a part of the 2 or more different optical material monomers is preferably 5 to 95 parts by mass, more preferably 20 to 80 parts by mass, and still more preferably 30 to 70 parts by mass, out of 100 parts by mass of the 2 or more different optical material monomers.

The following shows an example of a specific mode of the prepolymer process, but the prepolymer process in the production method B is not limited to the following mode.

(mode a)

The prepolymer step of the embodiment a is a step of mixing a part of 2 or more different monomers for optical materials with the whole of the polymerization catalyst, and polymerizing at least a part of the 2 or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer.

In the embodiment a, a part of the 2 or more different optical material monomers is preferably formed of all of 1 optical material monomer out of the 2 or more different optical material monomers and a part of the other optical material monomers other than the 1 optical material monomer.

(mode b)

The prepolymer step of the embodiment b is a step of mixing a part of 2 or more different monomers for optical materials with a part of a polymerization catalyst, and polymerizing at least a part of the 2 or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer.

When the production method B includes the prepolymer step of the embodiment B, the polymerizable composition for optical material production step described later is a step of adding at least the remaining part of the 2 or more different monomers for optical material and the remaining part of the polymerization catalyst to the mixture including the prepolymer, thereby obtaining a polymerizable composition for optical material containing the 2 or more different monomers for optical material, the prepolymer, and the polymerization catalyst.

In the embodiment b, it is preferable that 2 or more different optical material monomers contain an isocyanate compound, a part of 2 or more different optical material monomers contain a part of the isocyanate compound, and the remainder of 2 or more different optical material monomers contain the remainder of the isocyanate compound.

< procedure for viscosity adjustment >

The production method B preferably further includes a viscosity adjusting step of adjusting the viscosity of the mixture containing the prepolymer to 30mpa·s to 2000mpa·s after the prepolymer step and before the polymerizable composition for optical material production step.

By setting the viscosity of the mixture containing the prepolymer to be within the above range, the viscosity of the polymerizable composition for an optical material produced in the step of producing the polymerizable composition for an optical material can be set to be within an appropriate range from the viewpoint of suppressing the striae in the obtained optical material. As a result, the striae in the obtained optical material can be suppressed.

From the above viewpoints, the viscosity of the mixture containing the prepolymer is preferably 40 to 2000 mPas, more preferably 50 to 1800 mPas.

The viscosity was measured using a type B viscometer at 25 ℃ and 60rpm (rpm, revolutions per minute).

As a method of adjusting the viscosity of the mixture containing the prepolymer, there is no particular limitation.

For example, the viscosity of the mixture containing the prepolymer may be adjusted by adding a high-viscosity compound, heating, stirring, or the like.

The temperature at which the mixture containing the prepolymer is prepared is not particularly limited as long as the prepolymer can be obtained by polymerization. For example, the temperature may be 20℃to 50℃and 25℃to 45 ℃.

The stirring time for preparing the mixture containing the prepolymer is not particularly limited as long as the prepolymer can be obtained by polymerization. For example, the time period may be 30 minutes to 5 hours, and the time period may be 1 hour to 5 hours.

Specifically, the method for producing the prepolymer-containing mixture may be a method in which the prepolymer-containing mixture is produced while the viscosity is adjusted by stirring at 40℃for 3 hours.

Process for producing polymerizable composition for optical Material

The preparation method B comprises the following steps:

a step of producing a polymerizable composition for optical materials, wherein at least 2 or more different monomers for optical materials are added to a mixture containing a prepolymer, thereby obtaining a polymerizable composition for optical materials containing 2 or more different monomers for optical materials, a prepolymer, and a polymerization catalyst.

The step of producing the polymerizable composition for an optical material is a step of adding at least the remaining part of 2 or more different monomers for an optical material to a mixture containing a prepolymer, thereby obtaining a polymerizable composition for an optical material containing 2 or more different monomers for an optical material, a prepolymer, and a polymerization catalyst.

This prevents polymerization of the prepolymer and the remainder of the 2 or more different monomers for optical materials from occurring before the mixture containing the prepolymer and the remainder of the 2 or more different monomers for optical materials are mixed.

Therefore, by performing the process for producing the polymerizable composition for an optical material at an appropriate timing, for example, the operability when injecting the polymerizable composition for an optical material into a mold can be improved.

In the step of producing the polymerizable composition for optical materials, when at least the remaining part of 2 or more different monomers for optical materials are added to the mixture containing the prepolymer, the remaining part of 2 or more different monomers for optical materials may be mixed singly or may be mixed in a plurality of times.

The term "the remaining part of the 2 or more different optical material monomers" refers to a part of the 2 or more different optical material monomers that remains with respect to the "part of the 2 or more different optical material monomers" in the prepolymer step.

The "remainder of the 2 or more different monomers for optical materials" may be the following monomers for optical materials: the amount of the functional group that is polymerized with the polymerizable functional group of the prepolymer is an amount (i.e., equivalent) of the monomer for an optical material that is substantially polymerizable with all the polymerizable functional groups of the prepolymer.

From the viewpoint of improving the optical uniformity of the composition for an optical material, the remaining part of the 2 or more different monomers for an optical material preferably contains the same kind of monomers as those constituting the prepolymer.

The temperature at which the components are mixed is sometimes preferably lower than 25 ℃. However, in the case where the solubility of the additives such as the internal mold release agent and the above-mentioned components is poor, the above-mentioned components may be heated in advance, and the above-mentioned additives may be dissolved in the above-mentioned components.

Specific examples of the process for producing the polymerizable composition for optical material include the following.

First, an additive (for example, an internal mold release agent) is charged into a mixture containing a prepolymer to prepare a mixed solution. The mixture was stirred at 25℃for 1 hour, and after each component was completely dissolved, the mixture was degassed to obtain a 1 st mixture.

The remaining part of the monomer for an optical material and the remaining part of the polymerization catalyst as needed were stirred at 25℃for 30 minutes to completely dissolve the monomers, thereby obtaining a 2 nd mixed solution.

Then, the 1 st mixed solution and the 2 nd mixed solution were mixed, stirred, and then deaerated to obtain a uniform solution, thereby obtaining a polymerizable composition for an optical material.

< procedure of liquid delivery >)

The production method B may further include a liquid feeding step of feeding the polymerizable composition for optical material to a casting mold after the step of producing the polymerizable composition for optical material and before the curing step.

The liquid feeding step may be a step of feeding the polymerizable composition for an optical material to a casting mold while remixing the polymerizable composition for an optical material in a static mixer.

The liquid feeding step may be a step of feeding the polymerizable composition for an optical material to a casting mold while remixing the polymerizable composition for an optical material by a dynamic mixer.

Thus, the unevenness of the distribution of the polymerizable composition for an optical material can be eliminated during the transfer of the polymerizable composition for an optical material to the mold, and hence the streaks of the resulting cured product can be suppressed.

< curing Process >)

The preparation method B comprises the following steps:

and a curing step of curing 2 or more different monomers for optical materials in the polymerizable composition for optical materials to obtain an optical material as a cured product of the polymerizable composition for optical materials.

The specific mode, preferable mode, etc. of the curing process in the production method B are the same as the specific mode, preferable mode, etc. described in the item < curing process > in the production method a.

< prepolymer procedure 2 >

The preparation method B may further include the following steps in addition to the preparation step and the prepolymer step:

a 2 nd prepolymer step of mixing the remaining part of the 2 or more different monomers for optical materials with the remaining part of the polymerization catalyst, and polymerizing at least a part of the remaining part of the 2 or more different monomers for optical materials to obtain a 2 nd prepolymer, thereby obtaining a mixture containing the 2 nd prepolymer;

a step of producing a polymerizable composition for optical materials, wherein a mixture containing the 2 nd prepolymer is added to a mixture containing the prepolymer to obtain a polymerizable composition for optical materials containing the prepolymer, the 2 nd prepolymer, and the polymerization catalyst; and

and a curing step of curing the prepolymer and the 2 nd prepolymer in the polymerizable composition for an optical material to obtain an optical material as a cured product of the polymerizable composition for an optical material.

By the constitution described above, the preparation method B can obtain a mixture containing the prepolymer obtained in the prepolymer production step and a mixture containing the prepolymer 2 obtained in the prepolymer production step.

Thus, the viscosity of the mixture containing the prepolymer can be made close to that of the mixture containing the 2 nd prepolymer, and therefore, the two can be mixed more easily.

In the 2 nd prepolymer step, the monomer for optical material, the polymerization catalyst, the specific mode, the preferable mode, etc. are the same as those in the 2 nd prepolymer step.

In the case where the production method B includes the step of producing the 2 nd prepolymer, the step of producing the polymerizable composition for an optical material is a step of adding the mixture containing the 2 nd prepolymer to the mixture containing the prepolymer to obtain the polymerizable composition for an optical material containing the prepolymer, the 2 nd prepolymer, and the polymerization catalyst.

The mixture, specific embodiment, preferable embodiment, and the like containing the prepolymer in the step of producing the polymerizable composition for an optical material are the same as the specific embodiment, preferable embodiment, and the like in the step of producing the polymerizable composition for an optical material.

In the case where the production method B includes the 2 nd prepolymer step, the curing step is a step of curing the prepolymer in the polymerizable composition for an optical material and the 2 nd prepolymer to obtain an optical material as a cured product of the polymerizable composition for an optical material.

In the curing step, the prepolymer, the specific embodiment, the preferable embodiment, and the like are the same as those in the above-described < curing step >.

< annealing Process >)

The production method B may include an annealing step of annealing the cured polymerizable composition for optical materials, as required.

The preferred mode and the like of the annealing process in the production method B are the same as the preferred mode and the like of the annealing process in the production method a.

< other procedures >

Other steps may be provided for recipe B as needed.

The specific modes, preferable modes, and the like of the other steps in the production method B are the same as the specific modes, preferable modes, and the like of the other steps in the production method a.

< use of optical Material >

Specific examples, preferred specific examples, and the like of the use of the optical material in the production method B are the same as those of the use of the optical material in the production method a.

Embodiment 2 to the upper limit

Method for producing optical Material

The method for producing an optical material according to embodiment 2 includes the steps of:

a preparation step of preparing a polymerizable composition for an optical material, the polymerizable composition for an optical material containing 2 or more different monomers for an optical material; and a polymerization catalyst, wherein the content of the polymerization catalyst is 0.1 to 0.3 parts by mass based on 100 parts by mass of the total of the 2 or more different monomers for optical materials; and

The method for producing an optical material according to embodiment 2 is similar to the method for producing an optical material according to embodiment 1 except that the content of the polymerization catalyst is 0.1 to 0.3 parts by mass based on 100 parts by mass of the total of 2 or more different monomers for an optical material.

In the method for producing an optical material according to embodiment 2, details of specific examples, preferred specific examples, specific modes, preferred modes, and the like of each component are the same as those of specific examples, preferred specific examples, specific modes, preferred modes, and the like of each component in the method for producing an optical material according to embodiment 1.

Embodiment 2 of the present disclosure includes the following means.

A method for producing an optical material, comprising the steps of:

a preparation step of preparing a polymerizable composition for an optical material, the polymerizable composition for an optical material containing 2 or more different monomers for an optical material; and a polymerization catalyst, wherein the content of the polymerization catalyst is 0.05 to 2.0 parts by mass based on 100 parts by mass of the total of the 2 or more different monomers for optical materials; and

The method for producing an optical material according to claim 2-2 > and claim 2-1 > wherein the preparation step is a step of mixing the polymerization catalyst in advance in a part of the 2 or more different monomers for an optical material and then further mixing the rest of the 2 or more different monomers for an optical material to produce the polymerizable composition for an optical material.

The method for producing an optical material according to claim 2-3, wherein the curing step is a step of curing the polymerizable composition for an optical material by allowing the polymerizable composition for an optical material to stand in an enclosed space.

The method for producing an optical material according to any one of < 2-4 > to < 2-1 > - < 2-3 >, wherein the curing step is a step of curing the polymerizable composition for an optical material by allowing the polymerizable composition for an optical material to stand without heating from the outside.

The method for producing an optical material according to any one of < 2-5 > to < 2-1 > - < 2-4 >, wherein the curing step is a step of curing the polymerizable composition for an optical material by allowing the polymerizable composition for an optical material to stand for 2 to 10 hours.

The method for producing an optical material according to any one of < 2-6 > to < 2-1 > - < 2-5 >, wherein the 2 or more different monomers for an optical material contain an isocyanate compound and at least 1 active hydrogen compound selected from the group consisting of a polythiol compound having 2 or more mercapto groups, a hydroxythiol compound containing 1 or more mercapto groups and 1 or more hydroxyl groups, a polyol compound containing 2 or more hydroxyl groups, and an amine compound.

The method for producing an optical material according to 2-7 > the method of 2-6, wherein the isocyanate compound contains an isocyanate compound having no aromatic ring.

The method for producing an optical material according to any one of < 2-8 > to < 2-1 > - < 2-7 >, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of a basic catalyst having a pKa value of 4 to 8 and an organometallic catalyst.

The method for producing an optical material according to any one of < 2-9 > to < 2-1 > - < 2-8 >, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of an amine-based catalyst and an organotin-based catalyst.

The method for producing an optical material according to any one of < 2-10 > to < 2-1 > - < 2-9 >, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of 3, 5-lutidine, 2,4, 6-collidine, triethylenediamine, N-dimethylethanolamine, triethylamine, N-ethylmorpholine, dibutyltin dichloride, dimethyltin dichloride, dibutyltin dilaurate and dibutyltin diacetate.

2-11 > a polymerizable composition for optical materials, comprising 2 or more different monomers for optical materials and a polymerization catalyst, wherein the content of the polymerization catalyst is 0.1 to 0.3 parts by mass based on 100 parts by mass of the total of the 2 or more different monomers for optical materials.

Examples

The polythiol compound used in this example can be produced by the method described in International publication No. 2014/027665.

Example A >

Hereinafter, embodiments 1 and 2 of the present disclosure will be specifically described by way of example a, but embodiments 1 and 2 are not limited by these examples.

The method for measuring the viscosity in example A was the same as that described above.

The molded articles obtained in each example or comparative example were evaluated as follows.

(devitrification degree)

The molded article was produced by transmitting light from a light source (HAYASHI-REPIC CO., LTD. Luminar Ace LA-150A) in the dark. An image of light transmitted from the molded body is collected in an image processing device (Ube Information Systems inc.) and the collected image is subjected to shading. The degree of shading of the processed image is digitized for each pixel, and the average value of the numerical values of the degree of shading of each pixel is obtained to obtain the devitrification degree of the molded article.

The obtained devitrification was evaluated according to the following criteria.

A: the devitrification is less than 35.

B: the devitrification is 35 or more and less than 50.

C: the devitrification is 50 or more and less than 100.

D: the devitrification degree is 100 or more.

(tendon)

A molded body having a center thickness of 8mm and a diameter of 78mm was projected by an ultra-high pressure mercury lamp (model OPM-252HEG: manufactured by USHIO Inc.), and the transmitted image was visually observed and evaluated according to the following criteria.

A: no streaks were observed. Specifically, no streaks having a length of 1.0mm or more were observed visually within and outside the range of 15mm in radius from the center of the molded article.

B: while the striae were observed, they were generally allowable as articles. Specifically, although the beads having a length of 1.0mm or more were visually observed outside the range of 15mm in radius from the center of the molded body, the beads having a length of 1.0mm or more were not visually observed within the range of 15mm in radius from the center of the molded body, and were allowed to be substantially allowed as products.

C: the striae were observed and were not allowed as an article. Specifically, the beads having a length of 1.0mm or more were visually observed within and outside the range of 15mm of the radius from the center of the molded article.

(mold release Property)

The releasability of the molded article when the molded article was released from the molding die was evaluated according to the following criteria.

A: is peeled off even without applying force.

B: is peeled off when a force is applied.

C: although peeled off when a force is applied, there is a possibility that the mold or the lens may be broken.

D: cannot be peeled off even if a force is applied, and no article is obtained.

In examples A and B, the-Ea/R of each polymerization catalyst was as follows.

Dibutyl tin (II) -5737 dichloride

3, 5-lutidine-3397

2,4, 6-trimethylpyridine-4483

Example 1A

A mixture was prepared by charging 0.1 part by mass of ZelecUN [ internal mold release agent ] manufactured by Stepan, 1.5 parts by mass of 2- (2H-benzotriazol-2-yl) -4-tert-octylphenol [ ultraviolet absorber ] and 40.6 parts by mass of 2,5 (6) -bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane [ monomer for optical material ]. The mixture was stirred at 25℃for 1 hour to dissolve completely. Then, 23.9 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) [ monomer for optical material ] and 25.5 parts by mass of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane [ monomer for optical material ] were charged into the mixture, and stirred at 15℃for 5 minutes to prepare a homogeneous solution. The solution was deaerated at 400Pa for 60 minutes to obtain a 1 st mixed solution.

10.0 parts by mass of 2,5 (6) -bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane [ monomer for optical material ] and 0.3 parts by mass of dibutyltin (II) dichloride [ polymerization catalyst ] were stirred at 25℃for 30 minutes to dissolve completely, to obtain a 2 nd mixed solution.

Then, the 1 st mixed solution and the 2 nd mixed solution were mixed at 20℃to obtain a homogeneous solution, thereby obtaining a polymerizable composition for an optical material. The thixotropic ratios of the polymerizable compositions for optical materials are shown in table 1.

The solution was filtered with a 1. Mu.m PTFE filter and injected at a rate of 10 g/sec into a cavity of a casting mold composed of a 4-curve (4-curved) glass mold (upper mold) having a diameter of 78mm and a 4-curve glass mold (lower mold) having a diameter of 78mm, and having a cavity for lens production having a set center thickness of 8 mm. The cast article was placed in a heat-insulating container at 25℃and allowed to stand for 4 hours, and after heat-insulating polymerization, the cured molded article was released from the casting mold, and further annealed at 120℃for 2 hours to give a molded article (lens).

Further, as a result of measurement of properties of the obtained molded article, the refractive index (ne) was 1.596, the Abbe number (ve) was 39, the glass transition temperature (Tg) was 113℃and good physical properties were exhibited. The results of devitrification, striae and mold release are shown in Table 1.

Example 2A

A molded article was obtained in the same manner as in example 1A, except that the amount of the catalyst was set as described in table 1.

Further, as a result of measurement of properties of the obtained molded article, the refractive index (ne) was 1.598, the Abbe number (ve) was 39, the glass transition temperature (Tg) was 114℃and good physical properties were exhibited. The results of devitrification, striae and mold release are shown in Table 1.

Example 3A

A molded article was obtained in the same manner as in example 1A, except that 0.3 part by mass of dibutyltin (II) dichloride was changed to 0.25 part by mass of 3, 5-dimethylpyridine [ polymerization catalyst ] (pKa value=6.14).

Example 4A

A molded article was obtained in the same manner as in example 3A, except that the amount of the catalyst was set as described in table 1.

Further, as a result of measurement of properties of the obtained molded article, the refractive index (ne) was 1.598, the Abbe number (ve) was 39, the glass transition temperature (Tg) was 113℃and good physical properties were exhibited. The results of devitrification, striae and mold release are shown in Table 1.

Example 5A

A cured molded article was obtained in the same manner as in example 3A, except that the amount of the catalyst was set as described in table 1.

Further, as a result of measurement of properties of the obtained molded article, the refractive index (ne) was 1.597, the Abbe number (ve) was 39, the glass transition temperature (Tg) was 109℃and good physical properties were exhibited. The results of devitrification, striae and mold release are shown in Table 1.

Example 6A

A molded article was obtained in the same manner as in example 1A, except that 0.3 part by mass of dibutyltin (II) dichloride was changed to 0.13 part by mass of 2,4, 6-trimethylpyridine [ polymerization catalyst ] (pKa value=7.5).

Further, as a result of measurement of properties of the obtained molded article, the refractive index (ne) was 1.598, the Abbe number (ve) was 39, the glass transition temperature (Tg) was 112℃and good physical properties were exhibited. The results of devitrification, striae and mold release are shown in Table 1.

Example 7A

A molded article was obtained in the same manner as in example 1A, except that the types and amounts of the catalysts were set as described in table 1.

Further, as a result of measurement of properties of the obtained molded article, the refractive index (ne) was 1.598, the Abbe number (ve) was 39, the glass transition temperature (Tg) was 108℃and good physical properties were exhibited. The results of devitrification, striae and mold release are shown in Table 1.

Comparative example 1A

A polymerizable composition similar to that of example 1A was prepared and injected into the cavity of a casting mold, except that the amount of the catalyst was set as described in table 1. The casting mold filled with the polymerizable composition was put into a polymerization oven, and the temperature was gradually raised from 20℃to 130℃over 20 hours to carry out polymerization. After the polymerization was completed, the casting mold was taken out of the oven, the molded article was released from the cavity, and further, annealing was performed at 120℃for 2 hours to obtain a molded article.

Comparative example 2A

Polymerization was performed in the same manner as in comparative example 1A except that in comparative example 1A, the casting was cured by a polymerization program (temperature-raising program) that cured the casting for 4 hours. As a result of taking out the cavity immediately after polymerization, it was confirmed that the polymerizable composition swelled and overflowed from the cavity of the casting mold during the polymerization process. The cured molded article was released from the mold and further subjected to annealing at 120℃for 2 hours to obtain a molded article.

As a result of measurement of the properties of the obtained molded article, the refractive index (ne) was 1.596, the Abbe number (ve) was 39, and the glass transition temperature (Tg) was 113 ℃. The results of devitrification, striae and mold release are shown in Table 1.

After annealing, the appearance of the obtained molded article was observed (indoor vision), and as a result, bubbles were generated in the cured molded article, and many striae were also generated.

Comparative example 3A

Polymerization was carried out in the same manner as in example 1A except that the types and amounts of the catalysts were set as described in table 1, but were not cured. Since the resin was not cured, the devitrification and the like were not evaluated.

As described above, in the example in which the working time of the polymerization reaction is short, a lens of good quality is obtained.

On the other hand, in comparative example 1A, although a lens of good quality was obtained, the polymerization time was 20 hours, and a long time was required for completion of the polymerization.

In comparative example 2A, the polymerization time was set to 4 hours, and the quality of the obtained molded article was poor.

Example 8A

In the case of the embodiment of the present invention in example 1A,

the 1 st mixed solution was changed to a mixed solution prepared as described below;

0.3 parts by mass of dibutyltin (II) dichloride was changed to 0.15 parts by mass of dimethyltin (II) Dichloride (DMC); the method comprises the steps of,

a molded article (lens) was produced in the same manner as in example 1A, except that the cast article was placed in a heat-insulating container at 25 ℃ and left to stand for 5 hours, and additional heating was performed at 120 ℃ for 1 hour during the heat-insulating polymerization. In the production of the molded article, a graph showing the relationship between the elapsed time of the polymerization reaction and the temperature in the heat-insulating container is shown in fig. 1.

The method for producing the 1 st mixed solution in example 8A

First, reversacol Wembley Grey (0.036 parts by mass) of Vivimed corporation, reversacol Heath Green (0.060 parts by mass) of Vivimed corporation, peacock Blue (0.030 parts by mass) of Vivimed corporation, jalapeno Red (0.024 parts by mass) of Vivimed corporation, and HOSTAVIN PR-25 (0.075 parts by mass) of an ultraviolet absorber were dissolved in a composition (9.8 parts by mass) containing 2,5 (6) -bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane to prepare a mother liquor.

Next, a mixture was prepared by adding 2,5 (6) -bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane (30.05 parts by mass), the mother liquor obtained (10 parts by mass), ADEKA PLURONIC (registered trademark) L-64 manufactured by ADEKA Corporation (2.52 parts by mass), JP-506H (0.05 parts by mass) manufactured by urban and north chemical industry Co., ltd., pentaerythritol tetrakis (3-mercaptopropionate) (19.98 parts by mass), and 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane (27.25 parts by mass), respectively, to obtain a polymerizable composition for optical materials. The thixotropic ratio of the polymerizable composition for optical material was 1.0.

In the production of the molded article according to example 8A, the highest heat generation temperature in the polymerization process was 132 ℃ and the highest heat generation duration was 65 minutes. The molded article produced was not observed to be cloudy at all, and had good transparency. In addition, voids due to bubbles, cracks, and the like are not generated.

Example B >

Hereinafter, the recipe B of embodiment 1 will be specifically described by way of example B, but the recipe B of embodiment 1 is not limited to these examples.

The method for measuring the viscosity in example B was the same as that described above.

In example B, the amine content in the cured product was measured by the method described above. Specifically, the peak areas occurring in the retention time of 7.0 to 7.3 minutes were added, and the amine content was calculated using a previously prepared standard curve (y=0.00018x+6.43364, y: catalyst weight (. Mu.g), x: peak area).

(tendon)

The molded article was projected by an ultra-high pressure mercury lamp (model OPM-252HEG: manufactured by USHIO Inc.), and the transmitted image was visually observed, and evaluated according to the following criteria.

Example 1B

A mixed solution was prepared by charging 0.1 part by mass of an internal mold release agent [ internal mold release agent ] for MR, 1.5 parts by mass of Tinuvin329[ ultraviolet absorber ] and 40.6 parts by mass of a 2,5 (6) -bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane [ monomer for optical material ] manufactured by Sanjing chemical Co., ltd. The mixture was stirred at 25℃for 1 hour to dissolve completely. Then, 23.9 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) [ monomer for optical material ] and 25.5 parts by mass of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane [ monomer for optical material ] were charged into the mixture, and stirred at 25℃for 5 minutes to prepare a homogeneous solution. Further, 0.05 parts by mass of 3, 5-lutidine [ polymerization catalyst ] (pKa value=6.14) was charged into the obtained homogeneous solution, and the solution was stirred for 1 hour while deaerating at 400Pa and 25 ℃. The 1 st mixed solution, which is a mixture containing a prepolymer, is obtained by polymerizing a monomer for an optical material while adjusting the viscosity. The viscosity of the mixture containing the prepolymer is shown in table 2.

10.0 parts by mass of 2,5 (6) -bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane [ monomer for optical material ] and 0.15 parts by mass of 3, 5-dimethylpyridine [ polymerization catalyst ] were charged to prepare a mixed solution. The mixture was stirred at 25℃for 15 minutes to obtain a 2 nd mixture.

Then, the 1 st mixed solution and the 2 nd mixed solution were mixed at 20℃to obtain a polymerizable composition for an optical material.

Whether the prepolymer contained isocyanate groups or not is shown in Table 2.

Table 2 shows the value obtained by subtracting the refractive index B of the prepolymer raw material composition, which is a composition before forming a prepolymer and contains 2 or more different monomers for optical materials and a polymerization catalyst, from the refractive index a of the polymerizable prepolymer composition for optical materials (also referred to as "refractive index a-refractive index B").

The obtained polymerizable composition for an optical material was transferred to a casting mold (i.e., a casting mold) while being remixed in a static mixer.

The viscosity (also referred to as casting viscosity) of the polymerizable composition for an optical material to be transferred to the mold and cast was adjusted to the values shown in table 2.

During the transfer of the polymerizable composition for optical materials, the composition was injected into a cavity of a casting mold composed of a 4-curve or 6-curve glass mold (upper mold) having a diameter of 78mm and a 4-curve or 2-curve glass mold (lower mold) having a diameter of 78mm and having a cavity for lens production having a set center thickness as shown in Table 2 at a speed of 10 g/sec while being filtered with a 1. Mu.mPTFE filter.

The cast was placed in a heat-insulating container at 25℃and allowed to stand for 2 hours, and after heat-insulating polymerization, the cast was taken out of the heat-insulating container and further subjected to heat polymerization at 120℃for 1 hour.

The cured molded article was released from the casting mold, and further subjected to annealing treatment at 120℃for 2 hours to obtain a molded article (lens).

The amine content of the resulting molded article (i.e., cured product) is shown in Table 2.

Example 2B to example 4B

A molded article (lens) was obtained in the same manner as in example 1B, except that the polymerization catalyst amount and stirring time of the 1 st mixed solution in the prepolymer step were changed to the values shown in table 2, and the casting viscosity of the polymerizable composition for optical material was adjusted to the values shown in table 2.

Example 5B

A mixed solution was prepared by charging 0.1 part by mass of an internal mold release agent [ internal mold release agent ] for MR, 1.5 parts by mass of Tinuvin329[ ultraviolet absorber ] and 50.6 parts by mass of a 2,5 (6) -bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane [ monomer for optical material ] manufactured by Sanjing chemical Co., ltd. The mixture was stirred at 25℃for 1 hour to dissolve completely. Then, 1.7 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) [ monomer for optical material ] and 1.8 parts by mass of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane [ monomer for optical material ] were charged into the mixture, and stirred at 25℃for 5 minutes to prepare a homogeneous solution. Further, 0.2 parts by mass of 3, 5-lutidine [ polymerization catalyst ] was charged into the obtained homogeneous solution, and the mixture was stirred at 40℃for 3 hours, whereby the optical material monomer was polymerized while adjusting the viscosity, to obtain a prepolymer-containing mixture. The viscosity of the mixture containing the prepolymer is shown in table 2.

Then, the mixture containing the prepolymer was degassed at 400Pa and 25℃for 1 hour to obtain a 1 st mixed solution.

22.2 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) [ monomer for optical material ] and 23.7 parts by mass of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane [ monomer for optical material ] were charged to prepare a mixed solution, and the obtained mixed solution was degassed at 400Pa and 25℃for 1 hour to obtain a 2 nd mixed solution.

Using the obtained polymerizable composition for an optical material, the composition was transferred into a casting mold in the same manner as in example 1B, and the casting viscosity was adjusted to the values shown in table 2.

The casting was placed in a heat-insulating container at 25℃and allowed to stand for 2 hours, and after heat-insulating polymerization, the casting was taken out of the heat-insulating container and further subjected to heat polymerization at 120℃for 1 hour.

Example 6B to example 7B

A molded article (lens) was obtained in the same manner as in example 5B, except that the content of pentaerythritol tetrakis (3-mercaptopropionate) and 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane in the prepolymer step was changed to the values shown in table 2, and the casting viscosity of the polymerizable composition for an optical material was adjusted to the values shown in table 2.

Example 8B

A molded article (lens) was obtained in the same manner as in example 7B, except that the cast article was placed in a heat-insulating container at 25℃and allowed to stand for 3 hours, and the heat-insulating polymerization was performed, and then the cast article was taken out from the heat-insulating container and released from the mold.

Example 9B

A molded article (lens) was obtained in the same manner as in example 7B, except that the cast article was not subjected to heat-insulating polymerization, and the heat polymerization was performed over 3 hours from 30℃to 120 ℃.

Example 10B to example 11B

Example 12B

A molded article (lens) was obtained in the same manner as in example 5B, except that the polymerization catalyst was changed from 3, 5-lutidine to dibutyltin (II) dichloride, and the content of pentaerythritol tetrakis (3-mercaptopropionate) and 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane in the prepolymer step, the stirring time in the prepolymer step, the casting viscosity of the polymerizable composition for an optical material, and the time for adiabatic polymerization were changed to the values shown in Table 2.

Example 13B

A molded article (lens) was obtained in the same manner as in example 12B, except that the cast article was not subjected to heat-insulating polymerization, and the heat polymerization was performed over 3 hours with the lapse of time from 30℃to 120 ℃.

The types of monomers described in the tables are as follows.

a1: mixtures of 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane with 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane

a2: dicyclohexylmethane diisocyanate

a3:1, 3-bis (isocyanatomethyl) cyclohexane

b1: 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane

b2: pentaerythritol tetrakis (3-mercaptopropionate)

b3: mixtures of 5, 7-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithiaundecane, 4, 7-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithiaundecane, and 4, 8-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithiaundecane

b4: pentaerythritol tetrakis (2-mercaptoacetate)

b5:2, 5-bis (mercaptomethyl) -1, 4-dithiocyclohexane

As shown in table 2, for the example using the manufacturing method of the optical material including the steps of:

A preparation step of preparing a total of 100 parts by mass of 2 or more different monomers for optical materials and 0.010 to 2.0 parts by mass of a polymerization catalyst;

a prepolymer step of mixing at least a part of 2 or more different monomers for optical materials with at least a part of a polymerization catalyst, and polymerizing at least a part of the at least 2 or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer;

a step of producing a polymerizable composition for optical materials, wherein at least 2 or more different monomers for optical materials are added to a mixture containing a prepolymer, thereby obtaining a polymerizable composition for optical materials containing 2 or more different monomers for optical materials, a prepolymer, and a polymerization catalyst; and

In examples, the striae were more favorably suppressed in examples 2B to 4B and examples 6B to 11B in which the viscosity of the polymerizable composition for an optical material at the time of casting (i.e., casting viscosity) was 70mpa·s or more.

Example 14B

58.9 parts by mass of dicyclohexylmethane diisocyanate [ monomer for optical material ] and 1.5 parts by mass of Tinuvin329[ ultraviolet absorber ] were charged, and 0.1 part by mass of internal mold release agent [ internal mold release agent ] for MR, manufactured by Sanjing chemical Co., ltd was prepared. The mixture was stirred at 25℃for 1 hour to dissolve completely. Then, 4.1 parts by mass of a mixture of 5, 7-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithiaundecane, 4, 7-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithiaundecane and 4, 8-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithiaundecane was charged into the mixture, and the mixture was stirred at 25℃for 5 minutes to prepare a homogeneous solution. Further, 1.5 parts by mass of 3, 5-lutidine [ polymerization catalyst ] was charged into the obtained homogeneous solution, and the mixture was stirred at 40℃for 4 hours, whereby the monomer for an optical material was polymerized while adjusting the viscosity, to obtain a mixture containing a prepolymer. The viscosity of the mixture containing the prepolymer is shown in table 3.

37.0 parts by mass of a mixture of 5, 7-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithiaundecane, 4, 7-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithiaundecane and 4, 8-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithiaundecane was charged, and the mixture was degassed at 400Pa and 25℃for 1 hour to obtain a 2 nd mixture.

Using the obtained polymerizable composition for an optical material, the same procedure as in example 1 was used to convey the composition into a casting mold, and the casting viscosity was adjusted to the values shown in Table 3.

The cast was placed in a heat-insulating container at 25℃and allowed to stand for 3 hours, and after heat-insulating polymerization, the cast was taken out of the heat-insulating container and further subjected to heat polymerization at 130℃for 2 hours.

As shown in table 3, for the example using the manufacturing method of the optical material including the steps of:

Example 15B

48 parts by mass of 1, 3-bis (isocyanatomethyl) cyclohexane [ monomer for optical material ]1.5 parts by mass of Tinuvin329[ ultraviolet absorber ] and 0.18 part by mass of JP-506H (manufactured by Tokubei chemical Co., ltd.) were charged to prepare a mixed solution. The mixture was stirred at 25℃for 1 hour to dissolve completely. Then, 4.0 parts by mass of pentaerythritol tetrakis (2-mercaptoacetate) and 3.9 parts by weight of 2, 5-bis (mercaptomethyl) -1, 4-dithiacyclohexane were charged into the mixture, and stirred at 25℃for 5 minutes to prepare a homogeneous solution. Further, 0.1 part by mass of 3, 5-lutidine [ polymerization catalyst ] was charged into the obtained homogeneous solution, and the mixture was stirred at 40℃for 3 hours, whereby the optical material monomer was polymerized while adjusting the viscosity to obtain a prepolymer-containing mixture. The viscosity of the mixture containing the prepolymer is shown in table 5.

Into these mixed solution were charged 22.7 parts by mass of pentaerythritol tetrakis (2-mercaptoacetate) and 22.3 parts by weight of 2, 5-bis (mercaptomethyl) -1, 4-dithiane, and the mixed solution was degassed at 400Pa and 25℃for 1 hour to obtain a 2 nd mixed solution.

Using the obtained polymerizable composition for an optical material, the same procedure as in example 1 was used to convey the composition into a casting mold, and the casting viscosity was adjusted to the values shown in Table 5.

As shown in table 4, for the example using the manufacturing method of the optical material including the steps of:

The entire disclosures of japanese patent application 2020-01127 filed on 1 month 27 in 2020 and japanese patent application 2020-194660 filed on 11 month 24 in 2020 are incorporated herein by reference.

All documents, patent applications, and technical standards described in the present specification are incorporated by reference into the present specification to the same extent as if each document, patent application, and technical standard were specifically and individually described.

Claims

1. A polymerizable composition for optical materials, which comprises 2 or more different monomers for optical materials and a polymerization catalyst,

at least 1 of the 2 or more different monomers for optical materials is an isocyanate compound having no aromatic ring,

the content of the polymerization catalyst is more than 0.05 parts by mass and 2.0 parts by mass or less based on 100 parts by mass of the total of the 2 or more different monomers for optical materials,

the polymerizable composition for optical materials has a viscosity of 10 to 1000 mPas measured by a B-type viscometer at 25 ℃ and 60 rpm.

2. The polymerizable composition for optical materials according to claim 1, wherein the thixotropic ratio is 1.3 or less.

3. The polymerizable composition for optical materials according to claim 1 or 2, comprising:

2 or more different monomers for optical materials;

a polymerization catalyst; and

A prepolymer having a polymerizable functional group, which is a polymer of the 2 or more different monomers for optical materials.

4. The polymerizable composition for optical materials according to any one of claims 1 to 3, wherein the 2 or more different monomers for optical materials comprise at least 1 active hydrogen compound selected from the group consisting of a polythiol compound having 2 or more mercapto groups, a hydroxythiol compound comprising 1 or more mercapto groups and 1 or more hydroxyl groups, a polyol compound comprising 2 or more hydroxyl groups, and an amine compound.

5. The polymerizable composition for optical materials according to any one of claim 1 to 4, wherein the polymerization catalyst satisfies the following condition 1,

[ condition 1]

Ea/R is-7100 or more and-2900 or less,

ea is the activation energy calculated from Arrhenius curve by the reaction rate constant of the 2 or more different monomers for optical material at 2 or more different temperatures, and R is the gas constant (8.314J/mol/K).

6. The polymerizable composition for optical materials according to any one of claims 1 to 5, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of a basic catalyst having a pKa value of 4 to 8 and an organometallic catalyst.

7. A polymerizable prepolymer composition for optical materials, comprising: a prepolymer having a polymerizable functional group, the prepolymer being a polymer of 2 or more different monomers for an optical material; and a catalyst for the polymerization, wherein the catalyst comprises,

the polymerizable prepolymer composition for optical materials has a viscosity of 10 to 2000 mPas as measured by a B-type viscometer at 25 ℃ and 60 rpm.

8. The polymerizable prepolymer composition for optical materials according to claim 7, wherein the content of said polymerization catalyst is 0.1 to 4.0 parts by mass based on 100 parts by mass of the total of said prepolymers.

9. The polymerizable prepolymer composition for optical materials according to claim 7 or 8, wherein the 2 or more different monomers for optical materials comprise at least 1 active hydrogen compound selected from the group consisting of a polythiol compound having 2 or more mercapto groups, a hydroxythiol compound comprising 1 or more mercapto groups and 1 or more hydroxyl groups, a polyol compound comprising 2 or more hydroxyl groups, and an amine compound.

10. The polymerizable prepolymer composition for optical materials according to any one of claim 7 to 9, wherein the polymerization catalyst satisfies the following condition 1,

[ condition 1]

Ea/R is-7100 or more and-2900 or less,

11. The polymerizable prepolymer composition for optical materials according to any one of claims 7 to 10, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of a basic catalyst having a pKa value of 4 to 8 and an organometallic-based catalyst.

12. The polymerizable composition for optical materials according to any one of claims 1 to 6 or the cured product of the polymerizable prepolymer composition for optical materials according to any one of claims 7 to 11.

13. A method for producing an optical material, comprising the steps of:

The content of the polymerization catalyst is more than 0.05 parts by mass and 2.0 parts by mass or less relative to 100 parts by mass of the total of the 2 or more different monomers for optical materials;

a casting step of adjusting the viscosity of the polymerizable composition for an optical material measured with a B-type viscometer at 25 ℃ and 60rpm to 10 to 1000 mPas, and casting the composition into a mold; and

and a curing step of curing the polymerizable composition for optical material by polymerizing the 2 or more different monomers for optical material in the polymerizable composition for optical material in the mold.

14. A method for producing an optical material, comprising the steps of:

At least 1 of the 2 or more different monomers for optical materials is an isocyanate compound having no aromatic ring.

15. The method for producing an optical material according to claim 14, further comprising the step of:

16. The method for producing an optical material according to any one of claims 13 to 15, wherein the 2 or more different monomers for an optical material contain at least 1 active hydrogen compound selected from the group consisting of a polythiol compound having 2 or more mercapto groups, a hydroxythiol compound containing 1 or more mercapto groups and 1 or more hydroxyl groups, a polyol compound containing 2 or more hydroxyl groups, and an amine compound.

17. The method for producing an optical material according to any one of claim 13 to 16, wherein the polymerization catalyst satisfies the following condition 1,

[ condition 1]

Ea/R is-7100 or more and-2900 or less,

18. The method for producing an optical material according to any one of claims 13 to 17, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of a basic catalyst having a pKa value of 4 to 8, and an organometallic-based catalyst.

19. The method for producing an optical material according to any one of claims 13 to 18, wherein the polymerization catalyst comprises at least 1 selected from the group consisting of an amine-based catalyst and an organotin-based catalyst.

20. A cured product of 2 or more different optical monomers, wherein at least 1 of the 2 or more different optical monomers is an isocyanate compound having no aromatic ring, no beads having a length of 1.0mm or more are present within a range of 15mm from the radius of the center of the cured product, and the amine content is 0.03 mass% or more and 2.5 mass% or less as measured by gas chromatography mass spectrometry.